EP3202841B1 - Faserverstärkte flammhemmende polypropylenharzzusammensetzung und formartikel mit verwendung davon - Google Patents

Faserverstärkte flammhemmende polypropylenharzzusammensetzung und formartikel mit verwendung davon Download PDF

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Publication number
EP3202841B1
EP3202841B1 EP14902904.3A EP14902904A EP3202841B1 EP 3202841 B1 EP3202841 B1 EP 3202841B1 EP 14902904 A EP14902904 A EP 14902904A EP 3202841 B1 EP3202841 B1 EP 3202841B1
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Prior art keywords
polypropylene resin
fiber
weight
group
branched structure
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French (fr)
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EP3202841A4 (de
EP3202841A1 (de
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Masayuki Kabeya
Kazunobu Nakamori
Itsushi Imamura
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Japan Polypropylene Corp
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Japan Polypropylene Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Definitions

  • the present invention relates to a fiber-containing flame-retardant polypropylene resin composition, and more precisely, to a flame-retardant polypropylene resin composition containing a polypropylene resin having a specific long-chain branched structure, an organic flame retardant such as a phosphorus-containing flame retardant or the like and a fiber each in a specific amount, and preferably further containing a specific amount of any other polypropylene resin.
  • a flame-retardant composition containing a halogen flame retardant and an antimony compound is added to various types of polypropylene resin. This is advantageous in that the flame-retardant composition can exhibit flame retardance even when used in a relatively small amount, and hardly detracts from the advantageous performance of polypropylene resins.
  • flame-retardant materials are desired for automobile and home electric appliance materials, and these flame-retardant materials are also desired to have mechanical properties on the same level as that of conventional non-flame-retardant materials.
  • materials capable of giving an extremely high-level flame retardant effect and capable of satisfying mechanical properties (rigidity, impact), weather resistance and moldability are desired.
  • PTL 1 describes a flame-retardant resin composition having improved flame retardance by adding a small amount of tetrafluoroethylene resin (PTFE) to a thermoplastic resin to express an effect of drip protection (drip resistance) in firing the thermoplastic resin.
  • PTFE tetrafluoroethylene resin
  • PTLs 2 and 3 describes a technique of imparting mechanical properties, flame retardance and weather resistance by adding glass fibers to a flame-retardant material using a polyolefin and a nitrogen-containing phosphate.
  • PTL 4 describes a technique of expressing a drip protection effect in firing and expressing high flame retardance by adding a long-chain branched polypropylenic polymer to a polyolefin.
  • PTFE readily aggregates when given shear stress in kneading, and therefore the technology described in PTL 1 involves a risk of degradation of mechanical properties and flame retardance owing to aggregation of PTFE, and for the purpose of reducing the aggregation to a degree not having any influence on the mechanical properties, the amount of PTFE to be added must be minimized. As a result, reduction in flame retardance is inevitable owing to the reduction in the amount of PTFE added, and it is difficult to maintain flame retardance without degrading the mechanical properties.
  • An object of the present invention is to provide a flame-retardant polypropylene resin composition capable of expressing extremely high flame retardance to attain 5 VA in UL94-5V by satisfying both self-extinguishing property and drip resistance and given mechanical properties (rigidity, impact), weather resistance and moldability, which, however, has been difficult to attain according to an already-existing technique, and to provide a molded article using the composition.
  • the present inventors have assiduously studied for solving the above-mentioned problems, and, as a result, have found that, by combining a polypropylene resin having a specific long-chain branched structure and a non-halogen flame retardant such as an organic flame retardant, especially a phosphorus-containing flame retardant, and a fiber each in a specific amount, and preferably by further adding any other polypropylene resin thereto, a flame-retardant polypropylene resin composition capable of expressing extremely high flame retardance (5 VA in UL94-5V) in firing by satisfying both self-extinguishing property and drip resistance and given mechanical properties (rigidity, impact), weather resistance and moldability, can be obtained, and have completed the present invention.
  • a flame-retardant polypropylene resin composition capable of expressing extremely high flame retardance (5 VA in UL94-5V) in firing by satisfying both self-extinguishing property and drip resistance and given mechanical properties (rigidity, impact), weather resistance and moldability
  • a polypropylene resin composition comprising: a polypropylene resin (A) satisfying the following requirements (A-1) and (A-2); a fiber (B) satisfying the following requirement (B-1); and an organic flame retardant (C), the polypropylene resin composition satisfying the following requirement (I),
  • the polypropylene resin (A) contains a polypropylene resin (X) having a long-chain branched structure having the following characteristics (X-i) to (X-iv):
  • the fiber (B) is at least one type selected from a group consisting of a glass fiber and a carbon fiber,
  • the content of each component falls within a range that the polypropylene resin (A) is from 20 to 77 parts by weight, the fiber (B) is from 5 to 40 parts by weight, and the organic flame retardant (C) is from 18 to 40 parts by weight, and the total content of the polypropylene resin (A), the fiber (B) and the organic flame retardant (C) is 100 parts by weight.
  • the polypropylene resin composition in the first aspect of the invention wherein the polypropylene resin (A) further satisfies the following requirement (A-3), Requirement (A-3):
  • the polypropylene resin (A) contains the polypropylene resin (X) having a long-chain branched structure and the polypropylene resin (Y), and the ratio thereof is that the polypropylene resin (X) having a long-chain branched structure is from 10 to 99% by weight and the polypropylene resin (Y) is from 1 to 90% by weight (provided that the total of the polypropylene resin (X) having a long-chain branched structure and the polypropylene resin (Y) is 100% by weight).
  • the polypropylene resin composition in the first or second aspect of the invention wherein the organic flame retardant (C) is a phosphorus-containing flame retardant.
  • the polypropylene resin composition in any of the first to third aspects of the invention, wherein the fiber (B) is a glass fiber.
  • a molded article obtained by molding the polypropylene resin composition of any of the first to fourth aspects of the invention.
  • the polypropylene resin composition of the present invention containing a polypropylene resin having a specific long-chain branched structure, an organic flame retardant and a fiber each in a specific amount, and preferably containing any other polypropylene resin satisfies self-extinguishing property and drip resistance in firing in addition to excellent mechanical properties (rigidity, impact), weather resistance and moldability, and has extremely high-level flame retardance. Further, since the composition uses a non-halogen flame retardant, preferably a phosphorus-containing flame retardant or the like, as an organic flame retardant and does not use a chlorine, fluorine or bromine-containing compound, the environmental load thereof is extremely low.
  • the present invention relates to a polypropylene resin composition containing from 20 to 77 parts by weight of a polypropylene resin (A) containing a polypropylene resin (X) having a specific long-chain branched structure (hereinafter this may be simply referred to as component (X)) and satisfying a specific requirement (hereinafter this may be simply referred to as component (A)), from 5 to 40 parts by weight of a specific fiber (B) (hereinafter this may be simply referred to as component (B)), and from 18 to 40 parts by weight of an organic flame retardant (C) (hereinafter this may be simply referred to as component (C)) (provided that the total amount of the component (A), the component (B) and the component (C) is 100 parts by weight), in which the component (A) further contains, as a preferred component, a polypropylene resin (Y) (hereinafter this may be simply referred to as component (Y)), and the ratio of the components is that the component (X) is from 10 to
  • the polypropylene resin composition and the molded article formed by molding the composition of the present invention solve the problems with already-existing polypropylene resin compositions and molded articles formed by molding the composition, and are favorable to various molded articles, especially to automobile parts, electric parts, container packaging parts, building components, large-size components and others, as having extremely high-level flame retardance as well as excellent mechanical properties, weather resistance and moldability due to the incorporation of the fiber.
  • the polypropylene resin (A) for use in the present invention contains a polypropylene resin (X) having a specific long-chain branched structure (requirement (A-1)), and satisfies the requirement (A-2) in relation to the specific polypropylene resin (Y).
  • the resin contains the polypropylene resin (X) having a long-chain branched structure and the polypropylene resin (Y), and the ratio thereof is that the resin contains the polypropylene resin (X) having a long-chain branched structure is from 10 to 99% by weight and the polypropylene resin (Y) is from 1 to 90% by weight (provided that the total of the polypropylene resin (X) having a long-chain branched structure and the polypropylene resin (Y) is 100% by weight) (requirement (A-3)).
  • the polypropylene resin (X) having a long-chain branched structure for use in the present invention is characterized by having the following characteristics (X-i) to (X-iv).
  • the melt flow rate (MFR) of the polypropylene resin (X) having a long-chain branched structure for use in the present invention must fall within a range of from 0.1 to 30.0 g/10 min, and is preferably from 0.3 to 25.0 g/10 min, more preferably from 0.5 to 20.0 g/10 min.
  • MFR of the component (X) By defining MFR of the component (X) to fall within the range, the polypropylene resin composition of the present invention can exhibit good moldability while maintaining suitable flowability and, in addition, can have suitable melt tension, and therefore, the resin composition can have good drip resistance and can exhibit the effect of exhibiting high-level flame retardance.
  • the component (X) whose MFR is lower than the range is insufficient in flowability, and may cause some problems in production, for example, in that extruders in various moldings may require a too high load.
  • the component (X) whose MFR is higher than the range is insufficient in melt tension (viscosity) and therefore the drip resistance effect in firing would be poor, and the polypropylene resin composition would be unsuitable as a flame-retardant material.
  • MFR is measured according to Method A "Test Method for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics - Thermoplastic Plastics" under condition M (230°C, 2.16 kg load) in JIS K7210:1999. The unit is g/10 min.
  • the polypropylene resin (X) having a long-chain branched structure must have a relatively broad molecular weight distribution, and the molecular weight distribution Mw/Mn (where Mw means a weight-average molecular weight and Mn means a number-average molecular weight) determined by a gel permeation chromatography (GPC) must be from 3.0 to 10.0.
  • Mw means a weight-average molecular weight and Mn means a number-average molecular weight
  • GPC gel permeation chromatography
  • a preferred range of the molecular weight distribution Mw/Mn of the polypropylene resin (X) having a long-chain branched structure is from 3.5 to 8.0, more preferably from 4.1 to 6.0.
  • Mz/Mw (where Mz is a Z-average molecular weight) must be from 2.5 to 10.0.
  • a preferred range of Mz/Mw is from 2.8 to 8.0, more preferably from 3.0 to 6.0.
  • Resins having a broader molecular weight distribution could have more improved moldability, but those whose Mw/Mn and Mz/Mw each fall with the range have especially excellent moldability.
  • Mn, Mw and Mz are described in " Basis of Polymer Chemistry” (edited by the Society of Polymer Science, Japan, Tokyo Kagaku-Dojin Publishing Co., Ltd., 1978 ) or the like, and can be calculated from the molecular weight curve from GPC.
  • a specific measurement method through GPC employed in Examples in the present description is as follows.
  • PS polystyrene
  • 0.2 mL of a solution prepared by dissolving each compound in ODCB (containing 0.5 mg/mL of BHT) so as to be 0.5 mg/mL is injected to prepare a calibration curve.
  • the calibration curve uses a cubic expression method obtained through approximation according to a least-squares method.
  • polypropylene resin (X) having a long-chain branched structure must satisfy the following requirement (1).
  • MT is a melt tension measured using Toyo Seiki Seisakusho's Capillograph 1B, in which the capillary has a diameter of 2.0 mm and a length of 40 mm, the cylinder diameter is 9.55 mm, the cylinder extrusion rate is 20 mm/min, the take-up speed is 4.0 m/min and the temperature is 230°C, and the unit thereof is gram. Using other devices on the same level, MT can also be measured.
  • the resin may cut at a take-up speed of 4.0 m/min, and in the case, therefore, the take-up speed is lowered and the tension at the highest speed for possible take-up is referred to as MT.
  • the measurement condition and the unit for MFR are as mentioned above.
  • the definition is an index at which the polypropylene resin (X) having a long-chain branched structure could exhibit sufficient drip resistance in a firing test, and in general, MT has a correlation with MFR, and is therefore described as a relational equation with MFR.
  • JP-A 2003-25425 proposes the following relational expression as a definition of polypropylene having a high melt tension.
  • log MS > ⁇ 0.61 ⁇ log MFR + 0.82 230 ° C (Here, MS has the same meaning as MT.)
  • JP-A 2003-64193 proposes the following relational expression as a definition of polypropylene having a high melt tension. 11.32 ⁇ MFR ⁇ 0 ⁇ .7854 ⁇ MT 230 ° C
  • JP-A 2003-94504 proposes the following relational expression as a definition of polypropylene having a high melt tension.
  • MT 7 ⁇ .52 ⁇ MFR ⁇ 0 ⁇ .576 (MT is a value measured at 190°C, and MFR is a value measured at 230°C.)
  • the resin can be said to have a sufficiently high melt tension.
  • the polypropylene resin (X) having a long-chain branched structure and satisfying the requirement (1) is to be a resin excellent in drip resistance, and therefore when combined with a fiber (B) and an organic flame retardant (C) to be mentioned below, the resultant composition is especially useful as a flame-retardant material. More preferably, the resin satisfies the following requirement (1)', even more preferably the following requirement (1)".
  • the resin satisfies any of: log MT ⁇ ⁇ 0.9 ⁇ log MFR + 0.9 or MT ⁇ 15.
  • the resin satisfies any of: log MT ⁇ ⁇ 0.9 ⁇ log MFR + 1.1 or MT ⁇ 15.
  • MT is preferably 40 g or less, more preferably 35 g or less, even more preferably 30 g or less.
  • the stereoregularity of the polypropylene resin (X) having a long-chain branched structure for use in the present invention is higher, since the low-crystalline component to be a cause of stickiness and bleeding-out of the polypropylene resin composition and its molded article of the present invention could be small and since the resin could have high rigidity.
  • the low-crystalline component may be evaluated as a 25°C xylene-soluble component (CXS), and the content thereof must be less than 5.0% by weight relative to the total component (X), more preferably 3.0% by weight or less, even more preferably 1.0% by weight or less, still more preferably 0.5% by weight or less.
  • the lower limit is not specifically defined, but is generally 0.01% by weight or more, preferably 0.03% by weight or more.
  • CXS is defined to fall within the range, the rigidity of the polypropylene resin composition and its molded article of the present invention can be high, as described above, and in addition, stickiness and bleeding-out can be prevented.
  • the resin preferably has the following characteristic (X-v), and more preferably has the following characteristic (X-vi).
  • the characteristic (X-iv) and the characteristics (X-v) and (X-vi) to be mentioned below are all characteristics relating to stereoregularity.
  • the resin satisfies all the requirements (X-v) and (X-vi) in addition to the characteristic (X-iv).
  • the polypropylene resin (X) having a long-chain branched structure for use in the present invention preferably has high stereoregularity.
  • the height of stereoregularity can be evaluated by 13 C-NMR.
  • the resin has stereoregularity that the mm fraction of 3 propylene unit chains obtained in 13 C-NMR thereof is 95.0% or more.
  • the mm fraction is a ratio of 3 propylene unit chains in which the direction of the methyl branches in each propylene unit is the same, in any arbitrary 3 propylene unit chains having a head-tail junction, with respect to the polymer chain and the upper limit thereof is 100%.
  • the mm fraction is a value indicating that the stereostructure of the methyl groups in a polypropylene molecular chain is in isotactic control. A higher value of the mm fraction indicates that the resin is under higher control.
  • the flexural modulus that is an index of the rigidity of the polypropylene resin composition and its molded article of the present invention can be made high. In other words, when the mm fraction is smaller than the value shown below, the mechanical properties of the polypropylene resin composition and its molded article of the present invention may worsen, specifically, the flexural modulus that is an index of the rigidity thereof may lower.
  • the mm fraction is preferably 95.0% or more, more preferably 96.0% or more, even more preferably 97.0% or more, and as described above, the upper limit thereof is 100%.
  • a branching index g' is given by a ratio of the intrinsic viscosity [ ⁇ ]br of a polymer having a long-chain branched structure to the intrinsic viscosity [ ⁇ ]lin of a linear polymer having the same molecular weight as that of the branched polymer, that is, [ ⁇ ]br/[ ⁇ ]lin, and is smaller than 1 in the presence of a long-chain branched structure.
  • g' may be obtained as a function of an absolute molecular weight Mabs, for example, using GPC equipped with a light-scattering analyzer and a viscometer as mentioned below.
  • the polypropylene resin (X) having a long-chain branched structure for use in the present invention preferably has g' of from 0.30 to less than 1.00, when the absolute molecular weight Mabs thereof as measured through light scattering, Mabs is 1,000,000, more preferably from 0.55 to 0.98, even more preferably from 0.75 to 0.96, most preferably from 0.78 to 0.95.
  • the polypropylene resin (X) having a long-chain branched structure for use in the present invention may form a comb-shaped chain as the molecular structure thereof, from the polymerization mechanism, and when g' is defined to fall within the range, the melt tension can be controlled to fall within a suitable range, and therefore the drip resistance that is one evaluation index of flame retardance can be increased and, in addition, good moldability can be expressed.
  • the resin of the type is unfavorable for a flame-retardant material having high flame retardance that is targeted by the present invention.
  • the value of 1.00 means that the resin is not branched, and the resin of the type would have a low melt tension to lower the drip resistance, and therefore the resin of the type is also unfavorable for a flame-retardant material having high flame retardance that is targeted by the present invention.
  • the lower limit of g' is preferably the value mentioned above, and the reason is as follows.
  • g is a branching index defined by the rotation radius ratio of a polymer
  • ⁇ is a constant determined by the shape of the branch chain and a solvent
  • ⁇ is a ratio of the main chain of a comb-shaped chain
  • p is a mean branching number.
  • a branched polymer having g' that falls within the above range and having a structure similar to a comb-shaped chain is preferred, since the reduction in the melt tension thereof in repeated kneading is low, and therefore the physical properties and the moldability of the polymer of the type degrade little in reuse for molding of a recycled material that may be formed in a process of industrially producing molded articles, for example, lumber remnants in trimming during sheet or film formation, or members such as runners or the like in injection molding.
  • a GPC apparatus equipped with a differential refractometer (RI) and a viscometer Waters' Alliance GPCV2000 is used.
  • a light-scattering detector a multiangle laser light scattering detector (MALLS), Wyatt Technology's DAWN-E is used. The detector is connected in an order of MALLS, RI and Viscometer.
  • the mobile phase solvent is 1,2,4-trichlorobenzene (with BASF's antioxidant, Irganox 1076 added in an amount of 0.5 mg/mL).
  • the flow rate is 1 mL/min, and two columns of Tosoh's GMHHR-H(S) HT are used.
  • the temperature in the column, the sample injection part and each detector is 140°C.
  • the sample concentration is 1 mg/mL, and the injection amount (sample loop volume) is 0.2175 mL.
  • the branching index (g') is calculated as a ratio of the limiting viscosity ([ ⁇ ]br) of a sample measured with the above-mentioned viscometer, to the limiting viscosity ([ ⁇ ]lin) of a linear polymer measured separately, that is, ([ ⁇ ]br/[ ⁇ ]lin).
  • the radius of inertia of the polymer becomes smaller as compared with that of the linear polymer molecule having the same molecular weight.
  • the radius of inertia becomes small, the limiting viscosity also becomes small, and therefore, with introduction of a long-chain branched structure into a polymer, the ratio of the limiting viscosity ([ ⁇ ]br) of the branched polymer to the limiting viscosity ([ ⁇ ]lin) of the linear polymer having the same molecular weight, that is, ([ ⁇ ]br/[ ⁇ ]lin) becomes smaller.
  • the linear polymer having [ ⁇ ]lin a commercial homopolypropylene (Japan Polypropylene Corporation's Novatec PP (registered trademark), Grade: FY6) is used as the linear polymer having [ ⁇ ]lin.
  • the logarithm of [ ⁇ ]lin of a linear polymer is in a linear relationship to the logarithm of the molecular weight thereof, and this is known as a Mark-Houwink-Sakurada equation. Therefore, [ ⁇ ]lin can be obtained by suitable extrapolation on the low-molecular weight side or the high-molecular weight side.
  • the polypropylene resin satisfying the characteristic (X-iii) of (MT) ⁇ -0.9 ⁇ log(MFR) + 0.7 and satisfying g' ⁇ 1 with Mabs of 1,000,000 has a long-chain branched structure.
  • the production method for the resin is not specifically limited.
  • a preferred production method for the resin that satisfies all the high stereoregularity, the small low-crystalline component amount and the relatively broad molecular weight distribution as mentioned above, and preferably satisfies the requirements of the range of the branching index g', the high melt tension and others is a method of employing a macromer copolymerization method using a combined metallocene catalyst. Examples of the method are illustrated, for example, in JP-A 2009-57542 .
  • This method is for producing a polypropylene having a long-chain branched structure, using a combination of a catalyst component having a specific structure and having a macromer production capability, and a catalyst component having a specific structure, which has a high molecular weight and a macromer copolymerization capability.
  • the method it is possible to produce the polypropylene resin (X) having a long-chain branched structure and having the intended physical properties, using an industrially effective method of bulk polymerization or gas-phase polymerization, especially in single-stage polymerization under practicable pressure and temperature conditions using hydrogen as a molecular weight-regulating agent.
  • the branching efficiency must be increased by reducing the crystallinity by the use of a polypropylene component having a low stereoregularity, but according to the above-mentioned method, a polypropylene component having a sufficiently high stereoregularity can be introduced into side chains according to a simple method.
  • Employing the production method is preferred for satisfying the requirements (X-iv) to (X-v) relating to the high stereoregularity and the small low-crystalline component amount that are preferred for the polypropylene resin (X) having a long-chain branched structure for use in the present invention.
  • the polypropylene resin (X) having a long-chain branched structure there is mentioned a production method for a propylene polymer using the following catalyst components (A), (B) and (C) as the propylene polymerization catalyst.
  • R 11 and R 12 each independently represent a heterocyclic group having from 4 to 16 carbon atoms and containing nitrogen or oxygen and sulfur.
  • R 13 and R 14 each independently represent an aryl group having from 6 to 16 carbon atoms and optionally containing halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus or plural hetero elements selected from these, or a heterocyclic group having from 6 to 16 carbon atoms and containing nitrogen or oxygen and sulfur.
  • X 11 and Y 11 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having from 1 to 20 carbon atoms, a halogenohydrocarbon group having from 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having from 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having from 1 to 20 carbon atoms.
  • Q 11 represents a divalent hydrocarbon group having from 1 to 20 carbon atoms, or a silylene group or germylene group optionally having a hydrocarbon group with from 1 to 20 carbon atoms.
  • the heterocyclic group having from 4 to 16 carbon atoms and containing nitrogen or oxygen and sulfur for R 11 and R 12 is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group or a substituted 2-furfuryl group, and is more preferably a substituted 2-furyl group.
  • the substituent for the substituted 2-furyl group, the substituted 2-thienyl group and the substituted 2-furfuryl group includes an alkyl group having from 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, etc.; a halogen atom such as a fluorine atom, a chlorine atom, etc.; an alkoxy group having from 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, etc.; a trialkylsilyl group.
  • a methyl group and a trimethylsilyl group are preferred, and a methyl group is more preferred.
  • R 11 and R 12 each are especially preferably a 2-(5-methyl)-furyl group. Also preferably, R 11 and R 12 are the same.
  • the aryl group having from 6 to 16 carbon atoms and optionally containing halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus or plural hetero elements selected from these for R 13 and R 14 may have one or more substituents of a hydrocarbon group having from 1 to 6 carbon atoms, a silicon-containing hydrocarbon group having from 1 to 6 carbon atoms and a halogen-containing hydrocarbon group having from 1 to 6 carbon atoms, on the aryl cyclic skeleton within a range having from 6 to 16 carbon atoms.
  • R 13 and R 14 is a phenyl group, a 4-methylphenyl group, a 4-i-propylphenyl group, a 4-t-butylphenyl group, a 4-trimethylsilylphenyl group, a 2,3-dimethylphenyl group, a 3,5-di-t-butylphenyl group, a 4-phenylphenyl group, a chlorophenyl group, a naphthyl group, or a phenanthryl group, more preferably a phenyl group, a 4-i-propylphenyl group, a 4-t-butylphenyl group, a 4-trimethylsilylphenyl group, or a 4-chlorophenyl group.
  • R 13 and R 14 are the same.
  • X 11 and Y 11 are auxiliary ligands, and react with a promoter of the catalyst component (B) to form an active metallocene having olefin polymerization capability. Accordingly, so far as the object can be attained, X 11 and Y 11 are not specifically limited in point of the type of the ligand, and each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having from 1 to 20 carbon atoms, a halogenohydrocarbon group having from 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having from 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an alkylamide group having from 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, or a phosphorus-containing
  • Q 11 represents any of a divalent hydrocarbon group having from 1 to 20 carbon atoms, or a silylene group or germylene group optionally having a hydrocarbon group with from 1 to 20 carbon atoms, which bonds the two 5-membered rings.
  • two hydrocarbon groups exist on the silylene group or the germylene group they may bond to each other to form a cyclic structure.
  • Q 11 include an alkylene group such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, etc.; a silylene group; an arylalkylene group such as diphenylmethylene, etc.; an alkylsilylene group such as methylsilylene, dimethylsilylene, diethylsilylene, di(n-propyl)silylene, di(i-propyl)silylene, di(cyclohexyl)silylene, etc.; an (alkyl)(aryl)silylene group such as methyl(phenyl)silylene, etc.; an arylsilylene group such as diphenylsilylene, etc.; an alkyloligosilylene group such as tetramethyldisilylene, etc.; a germylene group; an alkylgermylene group corresponding to the divalent silylene group having a hydrocarbon group with from 1 to 20 carbon atoms, in which silicon is replaced by german
  • silylene group having a hydrocarbon group with from 1 to 20 carbon atoms or a germylene group having a hydrocarbon group with from 1 to 20 carbon atoms is preferred, and an alkylsilylene group or an alkylgermylene group is more preferred.
  • Preferred compounds of the compounds represented by the general formula (a1) are specifically exemplified hereinunder.
  • dichloro[1,1'-dimethylsilylenebis ⁇ 2-(5-methyl-2-furyl)-4-phenyl-indenyl ⁇ ]hafnium dichloro[1,1'-dimethylsilylenebis ⁇ 2-(5-methyl-2-furyl)-4-(4-methylphenyl)-indenyl ⁇ ]hafniu m
  • dichloro[1,1'-dimethylsilylenebis ⁇ 2-(5-methyl-2-furyl)-4-phenyl-indenyl ⁇ ]hafnium dichloro[1,1'-dimethylsilylenebis ⁇ 2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)-indenyl ⁇ ]hafniu m
  • dichloro[1,1'-dimethylsilylenebis ⁇ 2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl ⁇ ]hafniu m dichloro[1,1'-dimethylsilylenebis ⁇ 2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl
  • R 21 and R 22 each independently represent a hydrocarbon group having from 1 to 6 carbon atoms
  • R 23 and R 24 each independently represent an aryl group having from 6 to 16 carbon atoms and optionally containing halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus or plural hetero elements selected from these.
  • X 21 and Y 21 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having from 1 to 20 carbon atoms, a halogenohydrocarbon group having from 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having from 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having from 1 to 20 carbon atoms.
  • Q 21 represents a divalent hydrocarbon group having from 1 to 20 carbon atoms, or a silylene group or germylene group optionally having a hydrocarbon group with from 1 to 20 carbon atoms.
  • M 21 represents zirconium or hafnium.
  • R 21 and R 22 each independently represent a hydrocarbon group having from 1 to 6 carbon atoms, preferably an alkyl group, more preferably an alkyl group having from 1 to 4 carbon atoms. Specific examples of the group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl, etc. Methyl, ethyl and n-propyl are preferred.
  • R 23 and R 24 each independently represent an aryl group having from 6 to 16, preferably from 6 to 12 carbon atoms and optionally containing halogen, silicon, or plural hetero elements selected from these.
  • Preferred examples of the group include phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4-(2-fluoro-4-biphenylyl), 4-(2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3,5-dimethyl-4-t-butylphenyl,3,5-dimethyl-4-trimethylsilylphenyl, 3,5-dimethyl-4-t-butylphenyl, 3,5
  • X 21 and Y 21 are auxiliary ligands, and react with a promoter of the catalyst component (B) to form an active metallocene having olefin polymerization capability. Accordingly, so far as the object can be attained, X 21 and Y 21 are not specifically limited in point of the type of the ligand, and each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having from 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having from 1 to 20 carbon atoms, a halogenohydrocarbon group having from 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having from 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an alkylamide group having from 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, or a phosphorus-containing hydrocarbon group having from 1 to
  • Q 21 is a bonding group that crosslinks the two conjugated 5-membered ring ligands, representing a divalent hydrocarbon group having from 1 to 20 carbon atoms, a silylene group optionally having a hydrocarbon group with from 1 to 20 carbon atoms, or a germylene group optionally having a hydrocarbon group with from 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group.
  • the substituent bonding to silicon or germanium is preferably a hydrocarbon group having from 1 to 12 carbon atoms, and the two substituents may bond to each other.
  • Specific examples of the group include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, dimethylgermilene, diethylgermylene, diphenylgermylene, methylphenylgermylene, etc.
  • M 21 is zirconium or hafnium, preferably hafnium.
  • Non-limitative examples of the metallocene compounds represented by the general formula (a2) include the following.
  • dichloro[1,1'-dimethylsilylenebis ⁇ 2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl ⁇ ]hafnium dichloro[1,1'-dimethylsilylenebis ⁇ 2-methyl-4-(3-chloro-4-trimehtylsilylphenyl)-4-hydroazul enyl ⁇ ]hafnium
  • dichloro[1,1'-dimethylsilylenebis ⁇ 2-ethyl-4-(2-fluoro-4-biphenylyl)-4-hydroazulenyl ⁇ ]hafni um dichloro[1,1'-dimethylsilylenebis ⁇ 2-ethyl-4-(4-chloro-2-naphthyl)-4-hydroazulenyl ⁇ ]hafniu m
  • dichloro[1,1'-dimethylsilylenebis ⁇ 2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl ⁇ ]hafnium dichloro[1,1'-dimethylsilylenebis ⁇ 2-ethyl-4-(2-fluoro-4-biphenylyl)-4-hydroazulenyl ⁇ ]hafni um
  • the catalyst component (B) preferably used in producing the polypropylene resin (X) is an ion-exchanging layer silicate.
  • the ion-exchanging layer silicate (hereinafter this may be simply abbreviated as silicate) is a silicate compound having a crystal structure with planes each constituted by ionic bonding and piled up in parallel to each other by bonding force, in which the ions are exchangeable.
  • silicates are produced as a main ingredient of clay minerals, and therefore often contain any other impurities (quartz, cristobalite, etc.) than ion-exchanging layer silicates, and the silicate for use herein may contain such impurities.
  • silicates containing impurities would be better than pure silicates, and such composite forms are within the scope of the catalyst component (B).
  • the silicate for use in the present invention is not limited to natural products but may be any artificial synthetic product and may contain such synthetic products.
  • layer silicate examples include, for example, the following layer silicates as described in "Clay Mineralogy” written by Haruo Shiromizu, Asakura Publishing (1995).
  • Smectite group such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, etc.; vermiculite group such as vermiculite, etc.; mica group such as mica, illite, sericite, glauconite, etc.; attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite, etc.
  • the silicate is preferably one in which the main ingredient has a 2/1 structure, more preferably a smectite group, even more preferably montmorillonite.
  • the type of the interlayer cation is not specifically limited, but from the viewpoint of availability with ease and at low cost as an industrial material, a silicate in which the main ingredient of the interlayer cation is an alkali metal or an alkaline earth metal is preferred.
  • the ion-exchanging layer silicate of the catalyst component (B) in the present invention may be used directly as it is, not requiring any specific treatment, but preferably undergoes chemical treatment.
  • chemical treatment of the ion-exchanging layer silicate any of surface treatment of removing impurities from the surface or treatment having some influence on the clay structure is employable. Concretely, there are mentioned acid treatment, alkali treatment, salt treatment, organic matter treatment, etc.
  • impurities may be removed from surface, and in addition, a part or all of cations such as Al, Fe, Mg and the like in the crystal structure may be released.
  • the acid for use in acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid.
  • the treatment condition with salt and acid is not specifically limited, but in general, it is desirable that the salt or acid concentration is from 0.1 to 50% by weight, the treatment temperature is from room temperature to boiling point, and the processing time is from 5 minutes to 24 hours. Under the condition, at least a part of the substances that constitute at least one compound selected from a group consisting of ion-exchanging layer silicates are released.
  • salts and acids are used in the form of an aqueous solution thereof.
  • One prepared by combining the following acids and salts may be used as a treating agent. A combination of these acids and salts is also employable.
  • the salt to be used in salt treatment for ion exchange is a compound formed of a cation containing at least one atom selected from a group consisting of Group-1 to Group-14 atoms, and at least one anion selected from a group consisting of a halogen atom, an inorganic acid and an organic acid, more preferably a compound formed of a cation containing at least one atm selected from a group consisting of Group-2 to Group 14 atoms, and at least one anion selected from a group consisting of Cl, Br, I, F, PO 4 , SO 4 , NO 3 , CO 3 , C 2 O 4 , ClO 4 , OOCCH 3 , CH 3 COCHCOCH 3 , OCl 2 , O(NO 3 ) 2 , O(ClO 4 ) 2 , O(SO 4 ), OH, O 2 Cl 2 , OCl 3 , OOCH, OOCCH 2 CH 3 , C 2 H 4 O 4 and C 5 H 5 O 7
  • LiF LiF, LiCl, LiBr, LiI, Li 2 SO 4 , Li(CH 3 COO), LiCO 3 , Li(C 6 H 5 O 7 ), LiCHO 2 , LiC 2 O 4 , LiClO 4 , Li 3 PO 4 , CaCl 2 , CaSO 4 , CaC 2 O 4 , Ca(NO 3 ) 2 , Ca 3 (C 6 H 5 O 7 ) 2 , MgCl 2 , MgBr 2 , MgSO 4 , Mg(PO 4 ) 2 , Mg(ClO 4 ) 2 , MgC 2 O 4 , Mg(NO 3 ) 2 , Mg(OOCCH 3 ) 2 , MgC 4 H 4 O 4 , etc.
  • Ti(OOCCH 3 ) 4 Ti(CO 3 ) 2 , Ti(NO 3 ) 4 , Ti(SO 4 ) 2 , TiF 4 , TiCl 4 , Zr(OOCCH 3 ) 4 , Zr(CO 3 ) 2 , Zr(NO 3 ) 4 , Zr(SO 4 ) 2 , ZrF 4 , ZrCl 4 , ZrOCl 2 , ZrO(NO 3 ) 2 , ZrO(ClO 4 ) 2 , ZrO(SO 4 ), HF(OOCCH 3 ) 4 , HF(CO 3 ) 2 , HF(NO 3 ) 4 , HF(SO 4 ) 2 , HFOCl 2 , HFF 4 , HFCl 4 , V(CH 3 COCHCOCH 3 ) 3 , VOSO 4 , VOCl 3 , VCl 3 , VCl 4 , VBr 3 , etc.
  • Co(OOCCH 3 ) 2 Co(CH 3 COCHCOCH 3 ) 3 , CoCO 3 , Co(NO 3 ) 2 , CoC 2 H 4 , Co(ClO 4 ) 2 , Co 3 (PO 4 ) 2 , CoSO 4 , CoF 2 , CoCl 2 , NiCO 3 , Ni(NO 3 ) 2 , NiC 2 O 4 , Ni(ClO 4 ) 2 , NiSO 4 , NiCl 2 , NiBr 2 , etc.
  • Zn(OOCCH 3 ) 2 Zn(CH 3 COCHCOCH 3 ) 2 , ZnCO 3 , Zn(NO 3 ) 2 , Zn(ClO 4 ) 2 , Zn 3 (PO 4 ) 2 , ZnSO 4 , ZnF 2 , ZnCl 2 , AlF 3 , AlCl 3 , AlBr 3 , AlI 3 , Al 2 (SO 4 ) 3 , Al 2 (C 2 O 4 ) 3 , Al(CH 3 COCHCOCH 3 ) 3 , Al(NO 3 ) 3 , AlPO 4 , GeCl 4 , GeBr 4 , GeI 4 , etc.
  • alkali treatment or organic matter treatment may be carried out.
  • the treating agent to be used in alkali treatment include LiOH, NaOH, KOH, Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , Ba(OH) 2 , etc.
  • organic treatment agent for use in organic matter treatment examples include trimethylammonium, triethylammonium, N,N-dimethylanilinium, triphenylphosphonium, etc.
  • anion constituting the organic treatment agent examples include hexafluorophosphate, tetrafluoroborate, tetraphenylborate, etc., in addition to the anions exemplified hereinabove for those constituting salt treatment agents. However, these are not limitative.
  • treatment agents may be used either singly or as combined.
  • the treatment agents to be added at the start of treatment may be combined, or those to be added during treatment may be combined.
  • Chemical treatment may be carried out plural times, using one and the same treatment or using different treatment agents.
  • the ion-exchanging layer silicate generally contains adsorbed water and interlayer water. In the present invention, preferably, such adsorbed water and interlayer water are removed from the catalyst component (B) before use.
  • the heat treatment method for removing adsorbed water and interlayer water from the ion-exchanging layer silicate is not specifically limited, but must be so selected that interlayer water may not remain and that the treatment does not cause structural disorder.
  • the heating time is 0.5 hours or more, preferably 1 hour or more.
  • it is desirable that the water content of the dewatered catalyst component (B) is 3% by weight or less, preferably 1% by weight or less, when the water content of the component dewatered at a temperature of 200°C and under a pressure of 1 mmHg for 2 hours is 0% by weight.
  • ion-exchanging layer silicates prepared through salt treatment and/or acid treatment and having a water content of 3% by weight or less are especially preferred as the catalyst component (B).
  • the ion-exchanging layer silicate Before use for catalyst formation or as catalyst, the ion-exchanging layer silicate may be treated with a catalyst component (C) of an organic aluminium compound to be mentioned hereinunder, and the thus-treated silicate is preferred.
  • the amount of the catalyst component (C) relative to 1 g of the ion-exchanging layer silicate is not limited, but in general, the amount is 20 mmol or less, and is preferably from 0.5 mmol to 10 mmol.
  • the treatment temperature and the treatment time are not limited, and the treatment temperature is generally 0°C or higher and 70°C or lower, and the treatment time may be 10 minutes or more and 3 hours or less. After the treatment, the silicate may be washed, and washing it is preferred.
  • the solvent a hydrocarbon solvent that is the same as the solvent to be used in prepolymerization or slurry polymerization to be mentioned hereinunder, is used.
  • the catalyst component (B) is in the form of spherical particles having a mean particle size of 5 ⁇ m or more.
  • the particles natural substances or commercial products may be used directly as they are so far as they are spherical, or those whose form and particle size have been controlled through granulation, size classification or fractionation may also be used.
  • the granulation method employable here includes, for example, a stirring granulation method, and a spraying granulation method. Commercial products may also be used.
  • an organic matter an inorganic solvent, an inorganic salt and various binders may be used.
  • the spherical particles obtained in the manner as above preferably have a compression break strength of 0.2 MPa or more, more preferably 0.5 MPa or more, in order to prevent breakage or fine powder formation during a process of polymerization.
  • the particles have such a particle strength, the particle performance improving effect can be effectively exhibited especially in prepolymerization.
  • the catalyst component (C) is an organic aluminium compound.
  • the organic aluminium compound to be used as the catalyst component (C) is preferably a compound represented by a general formula, (AlR 31 q Z 3-q ) p .
  • R 31 represents a hydrocarbon group having from 1 to 20 carbon atoms
  • Z represents a halogen, hydrogen, an alkoxy group or an amino group.
  • q indicates an integer of from 1 to 3
  • p indicates an integer of 1 or 2.
  • R 31 is preferably an alkyl group.
  • Z is a halogen, it is preferably chlorine; when Z is an alkoxy group, it is preferably an alkoxy group having from 1 to 8 carbon atoms; and when Z is an amino group, it is preferably an amino group having from 1 to 8 carbon atoms.
  • organic aluminium compound examples include trimethylaluminium, triethylaluminium, tri-normal-propylaluminium, tri-normal-butylaluminium, tri-isobutylaluminium, tri-normal-hexylaluminium, tri-normal-octylaluminium, tri-normal-decylaluminium, diethylaluminium chloride, diethylaluminium sesquichloride, diethylaluminium hydride, diethylaluminium ethoxide, diethylaluminium dimethylamide, diisobutylaluminium hydride, diisobutylaluminium chloride, etc.
  • the catalyst may be formed by simultaneously or continuously adding the above-mentioned catalyst components (A) to (C) all at once or in plural times to a (pre)polymerization tank and are kept in contact with each other therein.
  • the components are brought into contact with each other in an aliphatic hydrocarbon or aromatic hydrocarbon solvent.
  • the contact temperature is not specifically limited, but is preferably from -20°C to 150°C.
  • any purposeful combination is employable, and especially preferred orders are shown below with respect to the constituent components.
  • the catalyst component (C) may be brought into contact with the catalyst component (A) or the catalyst component (B) before the catalyst component (A) and the catalyst component (B) are brought into contact with each other, or the catalyst component (C) may be brought into contact with both the catalyst component (A) and the catalyst component (B), or simultaneously with contact between the catalyst component (A) and the catalyst component (B), the catalyst component (C) may be brought into contact with the two, or the catalyst component may be brought into contact after the catalyst component (A) and the catalyst component (B) have been brought into contact with each other.
  • Preferred is a method where any of the catalyst component (A) and the catalyst component (B) is brought into contact with the catalyst component (C) before the former two are brought into contact with each other.
  • the resultant mixture may be washed with an aliphatic hydrocarbon or aromatic hydrocarbon solvent.
  • the amount of the catalyst components (A), (B) and (C) to be used is any arbitrary one.
  • the amount of the catalyst component (A) to be used is preferably within a range of from 0.1 ⁇ mol to 1,000 ⁇ mol relative to one g of the catalyst component (B), more preferably from 0.5 ⁇ mol to 500 ⁇ mol.
  • the amount of the catalyst component (C) relative to the catalyst component (A) is, as a molar ratio of the transition metal, preferably within a range of from 0.01 to 5 ⁇ 10 6 , more preferably from 0.1 to 1 ⁇ 10 4 .
  • the proportion of the component [A-1] (compound represented by the general formula (a1)) to the component [A-2] (compound represented by the general formula (a2)) is any arbitrary one within a range satisfying the above-mentioned characteristics of the propylene polymer, but preferably, the molar ratio of the transition metal in [A-1] to the total amount of the components [A-1] and [A-2] is 0.30 or more and 0.99 or less.
  • the component [A-1] produces a terminal vinyl macromer having a low molecular weight
  • the component [A-2] produces a high-molecular-weight form partially copolymerized with a macromer.
  • the proportion of the component [A-1] the mean molecular weight of the polymer to be formed, the molecular weight distribution, deviation to the high-molecular-weight side of the molecular weight distribution, an extremely high-molecular-weight component, and branching (amount, length, distribution) can be controlled, whereby the melt properties such as the rate of strain hardening, the melt tension and the melt ductility can be controlled.
  • the value For producing a propylene polymer having an extremely high rate of strain hardening, the value must be 0.30 or more, preferably 0.40 or more, more preferably 0.5 or more.
  • the upper limit is 0.99 or less, and for effectively obtaining the polypropylene resin (X) at a high catalyst activity, it is preferably 0.95 or less, more preferably within a range of 0.90 or less.
  • component [A-1] within the above-mentioned range makes it possible to control the balance between the mean molecular weight and the catalyst activity, relative to the hydrogen amount.
  • the catalyst in the present invention is subjected to prepolymerization treatment including minor polymerization through contact of the catalyst with an olefin.
  • the prepolymerization treatment prevents gel formation during the intended real polymerization.
  • the reason may be considered to be because the long-chain branching among the polymer particles could be uniformly distributed during polymerization, and because of the reason, the melt properties could be thereby improved.
  • the olefin to be used for prepolymerization is not specifically defined, and examples thereof include propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, etc.
  • the olefin feeding method any known method is employable, including a feeding method where an olefin is fed into a reactor while kept at a constant rate or under a constant pressure condition, a method of combination thereof, a method of stepwise changing the condition, etc.
  • the prepolymerization temperature and time is not specifically limited. Preferably, the temperature falls within a range of from -20°C to 100°C, and the time falls within a range of from 5 minutes to 24 hours.
  • the prepolymerized polymer amount is preferably from 0.01 to 100 relative to the catalyst component (B), more preferably from 0.1 to 50.
  • the catalyst component (C) may be added or may be added later. After prepolymerization, the catalyst may be washed.
  • a polymer such as polyethylene, polypropylene or the like, and a solid of an inorganic oxide such as silica, titania or the like may be made to be present in the reaction system, and the method is employable here.
  • the polymerization mode may be any and every one in which the olefin polymerization catalyst containing the catalyst component (A), the catalyst component (B) and the catalyst component (C) can be efficiently kept in contact with monomer.
  • slurry method using an inert solvent a so-called bulk method using propylene as a solvent but not substantially using an inert solvent
  • a solution polymerization method a gas-phase method where monomers are kept gaseous substantially not using a liquid solvent, etc.
  • a continuous polymerization or batchwise polymerization method is also employable.
  • two or more multistage polymerization is employable in addition to single-stage polymerization.
  • a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene or the like may be used either singly or as a mixture thereof.
  • the polymerization temperature is 0°C or higher and 150°C or lower.
  • the temperature is preferably 40°C or higher, more preferably 50°C or higher.
  • the upper limit is preferably 80°C or lower, more preferably 75°C or lower.
  • the temperature is preferably 40°C or higher, more preferably 50°C or higher.
  • the upper limit is preferably 100°C or lower, more preferably 90°C or lower.
  • the polymerization pressure is preferably 1.0 MPa or higher and 5.0 MPa or lower.
  • the pressure is preferably 1.5 MPa or higher, more preferably 2.0 MPa or higher.
  • the upper limit is preferably 4.0 MPa or lower, more preferably 3.5 MPa or lower.
  • the pressure is preferably 1.5 MPa or higher, more preferably 1.7 MPa or higher.
  • the upper limit is preferably 2.5 MPa or lower, more preferably 2.3 MPa or lower.
  • hydrogen may be used supplementarily for activity enhancement, in an amount as a molar ratio to propylene of 1.0 ⁇ 10 -6 or more and 1.0 ⁇ 10 -2 or less.
  • the mean molecular weight of the polymer to be formed, and in addition thereto, the molecular weight distribution, deviation to the high-molecular-weight side of the molecular weight distribution, an extremely high-molecular-weight component, and branching can be controlled, whereby the melt properties such as the rate of strain hardening, the melt tension and the melt ductility can be controlled, and accordingly, the melt properties that characterize polypropylene having a long-chain branched structure, such as MFR, rate of strain hardening, melt tension MT and melt ductility, can be thereby controlled.
  • hydrogen is used in an amount as a molar ratio to propylene of 1.0 ⁇ 10 -6 or more, more preferably 1.0 ⁇ 10 -5 or more, even more preferably 1.0 ⁇ 10 -4 or more.
  • the upper limit is preferably 1.0 ⁇ 10 -2 or less, more preferably 0.9 ⁇ 10 -2 or less, even more preferably 0.8 ⁇ 10 -2 or less.
  • ethylene and/or 1-butene is used in an amount of 15 mol% or less relative to propylene, more preferably 10.0 mol% or less, even more preferably 7.0 mol% or less.
  • a so-called macromer in which the polymer semiterminal shows mainly a propenyl structure is formed from the active species derived from the catalyst component [A-1] through specific chain-transfer reaction that is generally referred to as ⁇ -methyl elimination.
  • the macromer can form a polymer having a higher molecular weight, and is taken in the active species derived from the catalyst component [A-2] with better copolymerizability to thereby promoter macromer copolymerization.
  • the branch structure of the polypropylene resin having a long-chain branched structure to be formed would be mainly a comb-shaped chain.
  • One other additional characteristic feature of the polypropylene resin (X) having a long-chain branched structure for use in the present invention that is produced according to the above-mentioned method is that the rate of strain hardening ( ⁇ max(0.1)) thereof in measurement of elongation viscosity at a rate of strain of 0.1 s -1 is 6.0 or more.
  • the rate of strain hardening ( ⁇ max(0.1)) is an index of expressing a viscosity in melt, and when the value is large, the melt tension can be effectively increased. As a result, in a firing test, the resin can exhibit high-level drip resistance.
  • the rate of strain hardening is preferably 6.0 or more for expressing drip resistance, more preferably 8.0 or more.
  • the rate of strain hardening is preferably controlled to fall within the range, within which the resin can keep high-level drip resistance and can attain high-level flame retardance and can keep good moldability.
  • the elongation viscosity at a temperature of 180°C and at a strain rate of 0.1 s -1 is plotted on a double logarithmic graph in which the horizontal axis indicates time (t) and the vertical axis indicate elongation viscosity ⁇ E (Pa ⁇ sec). On the double logarithmic graph, the viscosity just before hardening is approximated in a straight line.
  • the elongation viscosity is plotted relative to the time, and the inclination at each time is determined.
  • the matter that the found data of the elongation viscosity are discrete is taken into consideration, and various averaging methods are used.
  • employable is a method where the inclination of adjacent data is read, and the moving average of some peripheral points is calculated.
  • the inclination tends to decrease with the lapse of time in a low strain region, but on the contrary, it tends to increase from a strain amount of about 1, and on the curve drawn by plotting the elongation viscosity relative to time, there exists an inflection point. Accordingly, within a strain amount range of from 0.1 to 2.5 or so, the point at which the inclination at each time as obtained in the above could be a minimum value is determined, and a contact line is drawn on the point, and the straight line is extrapolated until the strain amount could reach 4.0.
  • ⁇ max The maximum value ( ⁇ max) of the elongation viscosity ⁇ E until the strain amount could each 4.0 is determined, and the viscosity on the approximated straight line until that time is referred to as ⁇ lin.
  • ⁇ max/ ⁇ lin is defined as ⁇ max(0.1).
  • the polypropylene resin (X) having a long-chain branched structure for use in the present invention has high-level stereoregularity, by which molded articles having high rigidity can be produced.
  • the polypropylene resin (X) having a long-chain branched structure is a homopolypropylene (propylene homopolymer), or may be a propylene- ⁇ -olefin random copolymer with a small amount of any other commoner such as an ⁇ -olefin having from about 2 to 8 carbon atoms such as ethylene, 1-butene, 1-hexene or the like so far as the copolymer satisfies various characteristic features mentioned above.
  • the melting point thereof is preferably high.
  • the melting point measured through differential scanning calorimetry is preferably 145°C or higher, more preferably 150°C or higher.
  • the resin is preferred from the viewpoint of the heat resistance of products, and the upper limit of the melting point of the polypropylene resin (X) is generally 170°C.
  • the melting point can be measured through differential scanning calorimetry (DSC), in which a sample is once heated up to 200°C to erase the thermal history thereof, then cooled down to 40°C at a cooling rate of 10°C/min, and again heated at a heating rate of 10°C/min, and in this cycle, the endothermic peak top temperature is the melting point.
  • DSC differential scanning calorimetry
  • the polypropylene resin (Y) for use in the present invention is at least one polypropylene resin selected from a group consisting of a propylene homopolymer, a propylene- ⁇ -olefin block copolymer and a propylene- ⁇ -olefin random copolymer, not corresponding to the polypropylene resin (X) having a long-chain branched structure.
  • propylene- ⁇ -olefin block copolymer and propylene- ⁇ -olefin random copolymer may be simply referred to as "propylene- ⁇ -olefin copolymer".
  • the propylene- ⁇ -olefin copolymer preferred for use herein is a copolymer of propylene and a comonomer of an ⁇ -olefin having from 2 to 8 carbon atoms except propylene, or a random or block copolymer of propylene and an ⁇ -olefin in which the propylene content is from 70 to 99% by weight (that is, the comonomer content is from 1 to 30% by weight), more preferably the propylene content is 90% by weight or more.
  • a mixture of random copolymers or block copolymers that differ in the ⁇ -olefin therein is also usable.
  • ⁇ -olefins each having from 2 to 8 carbon atoms except propylene may be used either singly or as combined.
  • the propylene- ⁇ -olefm copolymer concretely includes a binary copolymer such as a propylene-ethylene copolymer, propylene-butene-1 copolymer, a propylene-pentene-1 copolymer, a propylene-hexene-1 copolymer or a propylene-octene-1 copolymer, a ternary copolymer such as a propylene-ethylene-butene-1 copolymer or a propylene-ethylene-hexene-1 copolymer, etc.
  • Preferred are a propylene-ethylene random copolymer, a propylene-ethylene-butene-1 random copolymer, etc.
  • the content of the ⁇ -olefin monomer in the propylene- ⁇ -olefin copolymer is generally from 0.01 to 30% by weight or so, preferably from 1 to 30% by weight or so, more preferably from 1 to 10% by weight or so.
  • the ⁇ -olefin having from 2 to 8 carbon atoms except propylene includes, for example, ethylene, 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, 1-octene, etc.
  • the melting point of the polypropylene resin (Y) is preferably from 100 to 170°C, more preferably from 160 to 165°C.
  • the melting point of a polypropylene resin may be suitably controlled depending on the propylene, the type of the ⁇ -olefin except propylene to be used as source materials, the copolymerization ratio, MFR, etc.
  • “melting point” is a melting peak temperature measured through with a differential scanning calorimeter (DSC).
  • the melt flow rate (hereinafter this may be expressed as MFR) according to JIS K7210 of the polypropylene resin (Y) for use in the present invention [measurement temperature 230°C, load 2.16 kg (21.18 N)] is preferably from 1.0 to 200 g/10 min, more preferably from 5.0 to 150 g/10 min, even more preferably from 10 to 100 g/10 min.
  • MFR melting point
  • the load in molding the polypropylene resin composition of the present invention increases so that the moldability thereof would worsen, and the appearance of the molded articles would worsen, for example, the molded articles would discolor; but on the contrary, when more than 200 g/10 min, the composition could not exhibit suitable drip resistance and the flame retardance thereof would worsen.
  • the isotactic pentad fraction (mmmm fraction) indicating the degree of crystallinity of the polypropylene resin (Y) is preferably 96% or more for use in the present invention, more preferably, the isotactic pentad fraction is 97% or more.
  • the isotactic pentad fraction is 96% or more, the rigidity and the heat resistance may increase, and the physical properties could be favorably better. This is presumed to be because, in the polypropylene resin (Y), the molecular orientation crystallinity could increase and in the polypropylene resin composition and its molded article of the present invention, orientation and uniform dispersion of the fiber (B) to be mentioned hereinunder could be thereby facilitated.
  • the degree of crystallinity of the polypropylene resin (Y) may be controlled by controlling the molecular weight distribution thereof through selection of the copolymerization ratio of the starting materials, and the catalyst to be used.
  • the isotactic pentad fraction is a value to be measured in 13 C-NMR (nuclear magnetic resonance), and is an isotactic fraction of the pentad units in the polypropylene molecular chain to be determined using a nuclear magnetic resonance spectrum ( 13 C-NMR) with isotopic carbon.
  • the isotactic pentad fraction is a fraction of propylene units of continuously isotactic-bonded 5 propylene monomer units.
  • the isotactic pentad units are determined as the intensity fraction of the mmmm peak in all the absorption peaks in the methyl carbon region of the 13 C-NMR spectrum, and, for example, an apparatus of JEOL's FT-NMR 270 MHz may be used.
  • the catalyst to be used for preparing the polypropylene resin (Y) for use in the present invention is not specifically limited, and any known catalyst is usable.
  • a so-called Ziegler-Natta catalyst of a combination of a titanium compound and an organic aluminium compound for example, described in Polypropylene Handbook (May 15, 1998, 1st ed., 1st run), etc.
  • a metallocene catalyst for example, described in JP-A 5-295022
  • the polymerization process for preparing the polypropylene resin (Y) for use in the present invention is not specifically limited, and any known polymerization process may be used.
  • a slurry polymerization method, a bulk polymerization method, a gas-phase polymerization method and the like may be used.
  • Any of a batch polymerization method or a continuous polymerization method may be used, and if desired, a two-stage, three-stage or more multistage continuous polymerization method may be used. By mechanically melt-kneading two or more propylene polymers, the resin may be produced.
  • polypropylene resin usable as the polypropylene resin (Y) various commercial products are put on the market by many companies. For example, there are mentioned Novatec Series products manufactured by Japan Polypropylene Corporation. Products having desired properties are selected from those commercial products and may be used herein.
  • the polypropylene resin (A) indispensably contains the polypropylene resin (X) having a long-chain branched structure.
  • the polypropylene resin (X) having a long-chain branched structure as one indispensable component in the polypropylene resin composition and its molded article of the present invention realizes the effect of maintaining high rigidity and good moldability, maintaining suitable flowability and, in addition, providing suitable melt tension to give good drip resistance and high-level flame retardance.
  • the polypropylene resin (A) is characterized by containing at least one polypropylene resin selected from a group consisting of the polypropylene resin (X) having a long-chain branched structure and the polypropylene resin (Y).
  • the polypropylene resin (X) having a long-chain branched structure has in the polypropylene resin composition and its molded article of the present invention, are further enhances or in a case where any other characteristics are given to the resin composition and its molded article, use of the polypropylene resin (Y) is effective.
  • the polypropylene resin (A) satisfies both the requirements (A-1) and (A-2), in which the polypropylene resin (X) having a long-chain branched structure is an indispensable component but use of the polypropylene resin (Y) is not always necessary depending on the object and the desired performance thereof.
  • the polypropylene resin (A) must satisfy the composition range of the requirement (I) to be described hereinunder in the polypropylene resin composition and its molded article of the present invention for solution to problem.
  • the polypropylene resin (X) having a long-chain branched structure is from 10 to 100% by weight and the polypropylene resin (Y) is from 0 to 90% by weight relative to the total, 100% by weight, of the polypropylene resin (X) having a long-chain branched structure and the polypropylene resin (Y), but preferably, the polypropylene resin (X) having a long-chain branched structure is from 10 to 99% by weight and the polypropylene resin (Y) is from 1 to 90% by weight.
  • the polypropylene resin (X) having a long-chain branched structure is from 15 to 90% by weight, even more preferably from 20 to 80% by weight, still more preferably from 25 to 75% by weight, and above all, further more preferably from 30 to 70% by weight.
  • the polypropylene resin (Y) is more preferably from 10 to 85% by weight, even more preferably from 20 to 80% by weight, still more preferably from 25 to 75% by weight, and above all, further more preferably from 30 to 70% by weight.
  • the fiber (B) for use in the present invention is at least one type of fiber (fibrous filler) selected from a group consisting of a glass fiber and a carbon fiber.
  • the fiber (B) not only improves the physical properties such as rigidity, impact strength and the like of the polypropylene resin composition and its molded article of the present invention but also contributes toward improving additional properties thereof such as heat resistance, dimensional stability (reduction in the linear expansion coefficient, etc.), low-contractility, scratch resistance, etc.
  • the fiber (B) is at least one type of fiber selected from a group consisting of a glass fiber and a carbon fiber as mentioned above, and preferably from the viewpoint of the advantageous effects of the present invention, and the easiness in production and the economic potential of the polypropylene resin composition and its molded article of the present invention, a glass fiber is preferred.
  • two or more types of the fiber (B) may be used as combined, and may be used in the form of a so-called master batch previously prepared by incorporating a relatively high concentration of the fiber (B) in the polypropylene resin (A).
  • any others not corresponding to the fiber (B), for example, glass beads, glass balloons and mica, as well as various inorganic or organic fillers not corresponding to the fiber (B) may be used along with the fiber (B) within a range not remarkably detracting from the advantageous effects of the present invention.
  • the glass fiber for use herein is not specifically limited, and regarding the type of glass for the fiber, for example, there are mentioned E glass, C glass, A glass, S glass, etc. Above all, E glass is preferred.
  • the production method for the glass fiber is not specifically limited, and the glass fiber may be produced various known production methods.
  • the fiber diameter of the glass fiber is preferably from 3 ⁇ m to 25 ⁇ m, more preferably from 6 ⁇ m to 20 ⁇ m.
  • the length is preferably from 2 mm to 20 mm.
  • the fiber diameter and the length may be obtained from the data measured with a microscope or a caliper.
  • the glass When the fiber diameter is less than 3 ⁇ m, the glass may be readily broken during production of the polypropylene resin composition and its molded article of the present invention and during molding the composition. On the other hand, when more than 25 ⁇ m, the effect of improving the rigidity and the impact strength of the polypropylene resin composition and its molded article of the present invention may degrade owing to the reduction in the aspect ratio of the fiber.
  • the fiber length is preferably from 2 mm to 20 mm as described above.
  • the fiber may worsen the physical properties such as rigidity and impact strength of the polypropylene resin composition and its molded article of the present invention, but on the other hand, when more than 20 mm, the moldability (flowability) may worsen.
  • the fiber length in this case may also be expressed as the length thereof in a case where the glass fiber is used as a source material directly as it is. However, this may not apply to a case where a large number of continuous glass fibers produced through melt extrusion to be mentioned below are aggregated and integrated to give glass-fiber containing pellets, and in general, glass roving is used. Two or more different types of glass fiber may be used as combined.
  • the glass fiber for use herein may be a surface-treated one or an untreated one.
  • the glass fiber is preferably surface-treated with an organic silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a zirconate coupling agent, a silicone compound, a higher fatty acid, a fatty acid metal salt, a fatty acid ester or the like.
  • the organic silane coupling agent for use for surface treatment includes, for example, vinyltrimethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, etc.
  • the titanate coupling agent includes, for example, isopropyltriisostearoyl titanate, isopropyltris(dioctylpyrophosphate) titanate, isopropyltri(N-aminoethyl) titanate, etc.
  • the aluminate coupling agent includes, for example, acetoalkoxyaluminium diisopropylate, etc.
  • the zirconate coupling agent includes, for example, tetra(2,2-diallyloxymethyl)butyl, di(tridecyl)phosphite zirconate; neopentyl(diallyl)oxy, trineodecanoyl zirconate.
  • the silicone compound includes silicone oil, silicone resin, etc.
  • the higher fatty acid for use for surface treatment includes, for example, oleic acid, capric acid, lauric acid, palmitic acid, stearic acid, montanic acid, kareic acid, linolic acid, rosin acid, linoleic acid, undecanoic acid, undecenoic acid, etc.
  • the higher fatty acid metal salt includes a sodium salt, a lithium salt, a calcium salt, a magnesium salt, a zinc salt, an aluminium salt or the like of a fatty acid having 9 or more carbon atoms, such as stearic acid, montanic acid, etc. Above all, calcium stearate, aluminium stearate, calcium montanate and sodium montanate are preferred.
  • fatty acid ester examples include a polyalcohol fatty acid ester such as a glycerin fatty acid ester, etc.; an alpha-sulfonic acid fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a sorbitan fatty acid ester, a polyethylene fatty acid ester, a sucrose fatty acid ester, etc.
  • the amount of the surface-treating agent to be used is not specifically limited. Preferably, the amount is from 0.01 parts by weight to 5 parts by weight relative to 100 parts by weight of the glass fiber, more preferably from 0.1 parts by weight to 3 parts by weight.
  • the glass fiber for use herein may be surface-treated for sizing with a sizing agent.
  • a sizing agent there are mentioned an epoxy sizing agent, an aromatic urethane sizing agent, an aliphatic urethane sizing agent, an acrylic sizing agent, a maleic anhydride-modified polyolefin sizing agent, etc.
  • the sizing agent must melt in melt-kneading with the polypropylene resin (A), and preferably, the agent melts at 200°C or lower.
  • the glass fiber may be used as a so-called chopped strand glass fiber prepared by cutting an original fiber into fiber pieces having a desired length.
  • the chopped strand glass fiber is preferably used.
  • glass fiber As specific examples of the glass fiber, there are mentioned those manufactured by JEOL (T480H), etc.
  • the glass fiber may also be used as "glass fiber-containing pellets" that are produced by previously aggregating and integrating an arbitrary amount of, for example, the polypropylene resin (A) and a large number of continuous glass fibers prepared through melt extrusion to give pellets, in which the length of the glass fibers in the pellets is substantially the same as the length of one side (extrusion direction) of the pellets, and use of the pellets is more preferred from the viewpoint of more enhancing the physical properties such as the rigidity and the impact strength of the polypropylene resin composition and its molded article of the present invention.
  • glass fiber-containing pellets that are produced by previously aggregating and integrating an arbitrary amount of, for example, the polypropylene resin (A) and a large number of continuous glass fibers prepared through melt extrusion to give pellets, in which the length of the glass fibers in the pellets is substantially the same as the length of one side (extrusion direction) of the pellets, and use of the pellets is more preferred from the viewpoint of more enhancing
  • substantially means concretely that, based on the number of all the glass fibers in the glass fiber-containing pellets, the length of the glass fibers is the same as the length (in the extrusion direction) of the glass fiber-containing pellets in a ratio of 50% or more, preferably 90% or more, and during the preparation of the pellets, the fibers are not almost broken.
  • the production method for the glass fiber-containing pellets is not specifically limited.
  • a method pulse molding method
  • a large number of continuous glass fibers are, while kept drawn through a crosshead die from a fiber rack, aggregated and integrated with an arbitrary amount of the component (A) in a mode of melt extrusion (immersion) in a melt state using a resin extruder, since the fibers are not almost broken during the method.
  • the length (in the extrusion direction) of the glass fiber-containing pellets is preferably from 2 mm to 20 mm like in the above, though depending on the glass fiber to be used.
  • the fiber may worsen the physical properties such as the rigidity and the impact strength of the polypropylene resin composition and its molded article of the present invention, while on the other hand, when more than 20 mm, the fiber may worsen the moldability (flowability) thereof.
  • the content of the glass fiber is preferably from 20% by weight to 70% by weight based on 100% by weight of the entire pellets.
  • the glass fiber-containing pellets in which the content of the glass fiber is less than 20% by weight are used in the present invention, they may worsen the physical properties such as the rigidity and the impact strength of the polypropylene resin composition and its molded article of the present invention, while on the other hand, in a case where those in which the content is more than 70% by weight are used, they may worsen the moldability (flowability) thereof.
  • the size and the type of the carbon fiber are not specifically limited, and ultrafine ones having a fiber diameter of 500 nm or less and called ultrafine carbon fibers may also be used.
  • the fiber diameter is from 2 ⁇ m to 20 ⁇ m, more preferably from 3 ⁇ m to 15 ⁇ m.
  • the carbon fiber would be readily broken during production and molding of the polypropylene resin composition and its molded article of the present invention, and if so, the effect of enhancing the physical properties such as the rigidity and the impact strength of the polypropylene resin composition and its molded article of the present invention may degrade.
  • the effect of enhancing the rigidity and the impact strength of the polypropylene resin composition and its molded article of the present invention may degrade owing to the reduction in the aspect ratio of the fiber.
  • the method for measurement of the fiber diameter is a known method, and for example, there is mentioned JIS R7607 (2000) (formerly JIS R7601) and a microscopic observation method.
  • the fiber length of the carbon fiber is preferably from 1 mm to 20 mm, more preferably from 3 mm to 10 mm.
  • the fiber length is the length of the carbon fiber that is used as a starting material directly as it is.
  • this does not apply to the case of "carbon fiber-containing pellets" produced by aggregating and integrating a large number of continuous carbon fibers prepared through melt extrusion, as described hereinunder.
  • roving fibers are used.
  • the fiber length is less than 1 mm
  • the final fiber length after production and molding of the polypropylene resin composition and its molded article of the present invention would be shorter so that the physical properties such as the rigidity and the impact strength of the polypropylene resin composition and its molded article of the present invention would be thereby worsened, but on the other hand, when more than 20 mm, the fibers may worsen the moldability (flowability) of the resin composition.
  • Two or more types of carbon fibers may be used as combined.
  • the type of the carbon fiber is not specifically limited as described above.
  • a PAN (polyacrylonitrile) carbon fiber produced from acrylonitrile as the main material a pitch carbon fiber produced from tar pitch as the main material, and a rayon carbon fiber, etc. Any of these are favorably used.
  • the applicability of these fibers in the present invention is high, but rather from the viewpoint of the composition purity and the uniformity, a PAN carbon fiber is preferred. One alone or two or more of these may be used either singly or as combined.
  • the production method for the carbon fiber is not specifically limited.
  • Carbon fiber generally has a tensile elastic modulus of from 200 GPa to 1000 GPa or so, but from the viewpoint of the strength and the economic potential of the polypropylene resin composition and its molded article of the present invention, those having from 200 GPa to 900 GPa are preferred, and those having from 200 GPa to 300 GPa are more preferred in the present invention.
  • Carbon fiber generally has a density of from 1.7 g/cm 3 to 5 g/cm 3 or so, but from the viewpoint of lightweightness and economic potential, those having a density of from 1.7 g/cm 3 to 2.5 g/cm 3 or so are preferred for use herein.
  • the measurement methods for the tensile elastic modulus and the density are known methods.
  • JIS R7606 for the tensile elastic modulus
  • JIS R7603 (1999) for the density
  • the carbon fiber may be used as a so-called chopped (strand-like) carbon fiber prepared by cutting an original fiber into fiber pieces having a desired length (hereinafter this may be simply referred to as CCF).
  • the fiber may be one subjected to sizing treatment with a sizing agent.
  • CCF is preferably used.
  • CCF include Mitsubishi Rayon's trade name "Pyrofil Chop”, Toray's trade name “Torayca Chop”, Toho Tenax's trade name "Besfight Chop” for PAN carbon fibers, and Mitsubishi Plastics' trade name "Dialead Chopped Fiber", Osaka Gas Chemical's trade name "Donacarbo Chop”, Kureha Chemical's "Kreca Chop” and the like for pitch carbon fibers.
  • the carbon fiber may also be used as "carbon fiber-containing pellets" that are produced by previously aggregating and integrating an arbitrary amount of, for example, the polypropylene resin (A) and a large number of continuous carbon fibers prepared through melt extrusion to give pellets, in which the length of the carbon fibers in the pellets is substantially the same as the length of one side (extrusion direction) of the pellets, and use of the pellets is more preferred from the viewpoint of more enhancing the physical properties such as the rigidity and the impact strength of the polypropylene resin composition and its molded article of the present invention.
  • carbon fiber-containing pellets that are produced by previously aggregating and integrating an arbitrary amount of, for example, the polypropylene resin (A) and a large number of continuous carbon fibers prepared through melt extrusion to give pellets, in which the length of the carbon fibers in the pellets is substantially the same as the length of one side (extrusion direction) of the pellets, and use of the pellets is more preferred from the viewpoint of more enhancing
  • substantially means concretely that, based on the number of all the carbon fibers in the carbon fiber-containing pellets, the length of the carbon fibers is the same as the length (in the extrusion direction) of the carbon fiber-containing pellets in a ratio of 50% or more, preferably 90% or more, and during the preparation of the pellets, the fibers are not almost broken.
  • the production method for the carbon fiber-containing pellets is not specifically limited.
  • a method pulse molding method
  • a large number of continuous carbon fibers are, while kept drawn through a crosshead die from a fiber rack, aggregated and integrated with an arbitrary amount of the component (A) in a mode of melt extrusion (immersion) in a melt state using a resin extruder, since the fibers are not almost broken during the method.
  • the length (in the extrusion direction) of the carbon fiber-containing pellets is preferably from 2 mm to 20 mm, though depending on the carbon fiber to be used.
  • the fiber may worsen the physical properties such as the rigidity and the impact strength of the polypropylene resin composition and its molded article of the present invention, while on the other hand, when more than 20 mm, the fiber may worsen the moldability (flowability) thereof.
  • the content of the carbon fiber is preferably from 20% by weight to 70% by weight based on 100% by weight of the entire pellets.
  • the carbon fiber-containing pellets in which the content of the carbon fiber is less than 20% by weight are used in the present invention, they may worsen the physical properties such as the rigidity and the impact strength of the polypropylene resin composition and its molded article of the present invention, while on the other hand, in a case where those in which the content is more than 70% by weight are used, they may worsen the moldability (flowability) thereof.
  • the organic flame retardant (C) for use in the present invention may be any organic flame retardant generally usable as flame retardants for polyolefins, and any of various organic flame retardants such as halogen-containing, phosphorus-containing or guanidine-containing flame retardants or melamine-cyanuric acid derivatives and the like are usable.
  • halogen-containing flame retardants include, for example, organic halogenated aromatic compounds such as halogenated diphenyl compounds, halogenated bisphenol compounds, halogenated bisphenol-bis(alkylether) compounds, halogenated phthalimide compounds, etc.
  • organic halogenated aromatic compounds such as halogenated diphenyl compounds, halogenated bisphenol compounds, halogenated bisphenol-bis(alkylether) compounds, halogenated phthalimide compounds, etc.
  • Halogenated bisphenol-bis(alkylether) compounds are used in many cases.
  • halogenated diphenyl compounds include, for example, halogenated diphenylether compounds, halogenated diphenylketone compounds, halogenated diphenylalkane compounds, etc. Above all, halogenated diphenylalkane compounds such as decabromodiphenylethane and the like are used in many cases.
  • halogenated bisphenol compounds include, for example, halogenated bisphenylalkanes, halogenated bisphenyl ethers, halogenated biphenyl thioethers, halogenated bisphenyl sulfones, etc.
  • halogenated bisphenyl thioethers such as bis(3,5-dibromo-4-hydroxyphenyl)sulfone and the like are used in many cases.
  • the halogenated bisphenol bis(alkylether) compounds include, for example, (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo-4-2,3-dibromopropoxyphenyl)metha ne, 1-(3,5-dibromo-4-2,3-dibromopropoxyphenyl)-2-(3-bromo-4-2,3-dibromopropoxyphenyl)et hane, 1-(3,5-dibromo-4-2,3-dibromopropoxyphenyl)-3-(3-bromo-4-2,3-dibromopropoxyphenyl)pr opane, 2,2-bis(3,5-dibromo-4-2,3-dibromopropoxyphenyl)propane, (3,5-dichloro-4-2,3-dibromopropoxyphenyl)-(3-chloro-4-2,3
  • brominated bisphenol A brominated aliphatic ether
  • brominated bisphenol S brominated aliphatic ether
  • chlorinated bisphenol A chlorinated aliphatic ether
  • chlorinated bisphenol S chlorinated aliphatic ether
  • especially etherified tetrabromobisphenol A and etherified tetrabromobisphenol S are used in many cases.
  • Examples of the etherified tetrabromobisphenol A include tetrabromobisphenol A-bis(2,3-dibromopropyl ether) and 2,2-bis(3,5-dibromo-4-2,3-dibromopropoxyphenyl)propane.
  • Examples of the etherified tetrabromobisphenol S include bis(3,5-dibromo-4-2,3-dibromopropoxyphenyl)sulfone.
  • halogen-containing flame retardants may be used either singly or as combined.
  • a halogenated diphenyl compound and a halogenated bisphenol compound may be used as combined.
  • any other organic flame retardant not corresponding to a halogen-containing flame retardant such as a phosphorus-containing flame retardant and the like, may be used along with the halogen-containing flame retardant.
  • halogen-containing flame retardants a bromine-containing flame retardant is used in many cases as the flame-retardant effect thereof is high.
  • phosphorus-containing flame retardants including organic phosphate compounds, phosphoric salt compounds and mixtures thereof are preferred from the viewpoint that halogen-containing flame retardants involve environmental load issues while such phosphorus-containing flame retardants are well dispersible in the polypropylene resin composition and its molded article of the present invention and can express a high flame-retardant effect.
  • phosphoric salt compounds are preferred.
  • organic phosphate compounds such as triphenyl phosphate, tricresyl phosphate, bisphenol A bisdiphenyl phosphate, resorcinol bisdiphenyl phosphate, etc.
  • phosphoric salt compounds such as ammonium polyphosphate, polyphosphoric melamine salt, polyphosphoric piperazine salt, orthophosphoric piperazine salt, pyrophosphoric melamine salt, pyrophosphoric piperazine salt, polyphosphoric melamine salt, orthophosphoric melamine salt, calcium phosphate, magnesium phosphate, etc., and their mixtures, etc.
  • the content of each component falls within a range that the polypropylene resin (A) is from 20 to 77 parts by weight, the fiber (B) is from 5 to 40 parts by weight, and the organic flame retardant (C) is from 18 to 40 parts by weight, and the total content of the polypropylene resin (A), the fiber (B) and the organic flame retardant (C) is 100 parts by weight (requirement (I)).
  • the polypropylene resin composition and its molded article of the present invention can satisfy both self-extinguishing property and drip resistance and can express extremely high-level flame retardance, which, however, has heretofore been difficult in conventional technology, and can attain 5VA in UL94-5V while given mechanical properties (rigidity, impact), weather resistance and moldability.
  • the polypropylene resin (A) is preferably from 35 to 70 parts by weight, more preferably from 38 to 65 parts by weight, even more preferably from 40 to 60 parts by weight, especially preferably from 45 to 50 parts by weight.
  • the fiber (B) is preferably from 7 to 38 parts by weight, more preferably from 8 to 35 parts by weight, even more preferably from 10 to 30 parts by weight.
  • the mechanical properties (rigidity, impact) of the polypropylene resin composition and its molded article of the present invention may worsen.
  • the moldability (flowability) may degrade.
  • the compounded amount of the fiber (B) is the net weight thereof, and for example, in a case where the above-mentioned glass fiber-containing pellets are used, the amount is calculated on the basis of the actual content of the fiber (B) contained in the pellets.
  • the organic flame retardant (C) is preferably from 19 to 38 parts by weight, more preferably from 20 to 35 parts by weight, even more preferably from 23 to 32 parts by weight, especially preferably from 25 to 30 parts by weight.
  • the compounded amount of the organic flame retardant (C) is lower than the range defined in the present invention, sufficient flame retardance could not be realized, but on the other hand, when higher than the range defined in the present invention, it would worsen the moldability and would cause economic disadvantage.
  • the blending amount of each component of the polypropylene resin (A), the fiber (B) and the organic flame retardant (C) may be selected from the range of each component defined in the present invention so that the total amount of the polypropylene resin (A), the fiber (B) and the organic flame retardant (C) could be 100 parts by weight.
  • any ordinary optional additive component (D) may be incorporated within a range not significantly detracting the advantageous effects of the present invention, for example, for further enhancing the advantageous effects of the present invention and for giving any other effects, in addition to the polypropylene resin (A), the fiber (B) and the organic flame retardant (C).
  • the optional component includes a molecular weight depressant such as peroxides, etc.; a colorant such as pigments, etc.; an antioxidant such as modified polyolefins, phenolic, phosphorus-containing, sulfur-containing antioxidants, etc.; a light stabilizer such as hindered amines, etc.; a UV absorbent such as benzotriazoles, etc.; a nucleating agent such as sorbitols, etc.; an antistatic agent such as nonionic antistatic agents, etc.; a dispersant such as organic metal salts, etc.; a metal inactivator such as nitrogen compounds, etc.; an antibacterial/antifungal agent such as thiazoles, etc.; a plasticizer, a neutralizing agent, a lubricant, an elastomer (rubber component), a flame-retardant promoter such as metal oxides, etc.; any other polyolefin resin than the polypropylene resin (A), a thermoplastic resin such as thermo
  • the compounded amount of the optional additive component (D) is not specifically limited, but is generally from 0 to 4.0 parts by weight or so relative to 100 parts by weight of the total amount of the polypropylene resin (A), the fiber (B) and the organic flame retardant (C).
  • molecular weight depressant for example, various types of organic peroxides, those referred to as a decomposition (oxidation) accelerator and the like are usable, and organic peroxides are preferred.
  • organic peroxides there are mentioned one or more selected from a group of benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexyne-3, t-butyl diperadipate, t-butylperoxy-3,5,5-trimethylhexanoate, methylethyl ketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, 1,3-bis(t
  • the colorant such as inorganic or organic pigments is effective for conferring and improving color appearance, flaw resistance, visual appearance, texture; product quality, weather resistance and durability of the polypropylene resin composition and its molded article of the present invention.
  • the inorganic pigments include carbon black such as furnace carbon and ketjen carbon; titanium oxides; iron oxides (such as colcothar); chromic acids (such as chrome yellow); molybdenum acids; selenium sulphides; ferrocyanides and the like
  • the organic pigments include azo pigments such as a slightly soluble azo lake, a soluble azo lake, an insoluble azo chelate, a condensation azo chelate and other azo chelates; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; threne pigments such as anthraquinone, perynone, perylene and thioindigo; lake dyes; quinacridone dyes; dioxazine dyes; isoindolinone dyes and the like. Aluminium flakes or pearl pigments may be added in order to confer metallic or pearl appearance. Dyes may also be added.
  • the light stabilizer and the UV absorbent such as hindered amine compounds, benzotriazol compounds, benzophenone compounds and salicylate compounds are effective for conferring and improving weather resistance and durability of the polypropylene resin composition and its molded article of the present invention.
  • hindered amine compounds may include a condensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethyl piperidine; poly[[6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazin-2,4-diyl][(2,2,6,6-tetramethyl-4-piperid yl)imino]hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)imino]]; tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate; tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate; bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate; bis-2,2,6,6-tetramethyl-4-piperid
  • the light stabilizer and the ultraviolet absorbing agent are used in combination because the effect for improving weather resistance and durability is enhanced.
  • the antioxidant such as phenol, phosphorus and sulfur antioxidants is effective for conferring and improving thermal stability, process stability and thermal aging resistance of the polypropylene resin composition and its molded article of the present invention.
  • the antistatic agent such as nonionic and cationic antistatic agents is effective for conferring and improving antistatic property of the polypropylene resin composition and its molded article of the present invention.
  • the metal oxides includes zinc oxide, iron oxide, aluminium oxide, molybdenum oxides, etc. More preferred metal oxides are zinc oxide and iron oxide, and those having a mean particle size of 30 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 1 ⁇ m or less are preferred. A metal oxide whose mean particle size is larger than 30 ⁇ m is poorly dispersible in the polyolefin resin (A) and therefore could not realize high-level flame retardance.
  • the amount of the metal oxide, if used, is preferably from 0.05 to 5 parts by weight relative to 100 parts by weight of the polypropylene resin (A), the fiber (B) and the organic flame retardant (C), more preferably from 0.1 to 3 parts by mass.
  • the amount is less than 0.05 parts by weight, a synergistic flame-retardant effect by sufficient addition could not be realized, but on the other hand, when a compounding amount of more than 5 parts by weight is uneconomical and disadvantageous.
  • the modified polyolefin is an acid modified polyolefin and/or a hydroxy modified polyolefin and is characterized in that it effectively confers functions such as mechanical properties (especially rigidity, impact strength) in the present invention.
  • the acid modified polyolefin is not particularly limited and may be any conventional well known acid modified polyolefins.
  • the acid modified polyolefin is the one obtained by graft copolymerization of polyolefins such as polyethylenes, polypropylenes, ethylene- ⁇ -olefin copolymers, ethylene- ⁇ -olefin-unconjugated diene compound copolymers (EPDM and the like), ethylene-aromatic monovinyl compound-conjugated diene compound copolymerized rubbers and the like with unsaturated carboxylic acids such as maleic acid or maleic anhydride so as to effect modification.
  • polyolefins such as polyethylenes, polypropylenes, ethylene- ⁇ -olefin copolymers, ethylene- ⁇ -olefin-unconjugated diene compound copolymers (EPDM and the like), ethylene-aromatic monovinyl compound-conjugated diene compound copolymerized rubbers and the like with unsaturated carboxylic acids such as maleic acid or maleic anhydride so as
  • the graft copolymerization may be carried out by, for example, reaction of the polyolefin in a suitable solvent with the unsaturated carboxylic acid in the presence of a radical generating agent such as benzoyl peroxide.
  • a radical generating agent such as benzoyl peroxide.
  • the component such as the unsaturated carboxylic acid and a derivative thereof may also be introduced in the polymer chain by random or block copolymerization using a monomer for the polyolefin.
  • the unsaturated carboxylic acid used for modification may include, for example, compounds having a polymerizable double bond and containing a carboxyl group and optionally a functional group including hydroxyl and amino groups such as maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid.
  • the derivative of the unsaturated carboxylic acid may include acid anhydrides, esters, amides, imides and metal salts thereof which may specifically include maleic anhydride, itaconic anhydride , methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, maleimide, N-butylmaleimide, sodium methacrylate and the like.
  • Maleic anhydride is preferred.
  • the graft reaction may be carried out, for example, by using an organic peroxide such as dialkyl peroxides including di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 and the like; peroxy esters including t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyisopropylcarbonate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexyne-3 and the like; diacyl peroxides including benzoyl peroxide and the like; hydroperoxides such as diisopropylbenzene hydro
  • the degree of acid modification (which may also be referred to as grafting percentage) of the acid modified polyolefin is not particularly limited and is preferably, in terms of maleic anhydride, 0.05 to 10% by weight and more preferably 0.07 to 5% by weight.
  • the preferable acid modified polyolefin may include maleic anhydride modified polypropylenes.
  • the hydroxy modified polyolefin is a modified polyolefin containing a hydroxyl group.
  • the modified polyolefin may contain the hydroxyl group at any position, for example at the terminal(s) of a main chain or in a side chain.
  • the olefin resin included in the hydroxy modified polyolefin may be exemplified by, for example, homopolymers or copolymers of an ⁇ -olefin such as ethylene, propylene, butene, 4-methylpentene-1, hexene, octene, nonene, decene, dodecene and the like and copolymers of the ⁇ -olefin and a copolymerizable monomer.
  • ⁇ -olefin such as ethylene, propylene, butene, 4-methylpentene-1, hexene, octene, nonene, decene, dodecene and the like
  • Preferred hydroxy modified polyolefin may be exemplified by hydroxy modified polyethylenes (such as low, medium or high density polyethylenes, linear low density polyethylenes, ultra-high molecular weight polyethylenes, ethylene-(meth)acrylic ester copolymers and ethylene-vinyl acetate copolymers), hydroxy modified polypropylenes (such as polypropylene homopolymers including isotactic polypropylenes, random copolymers of propylene and an ⁇ -olefin (for example, ethylene, butene and hexane), propylene- ⁇ -olefin block copolymers), hydroxy modified poly(4-methylpentene-1) and the like.
  • hydroxy modified polyethylenes such as low, medium or high density polyethylenes, linear low density polyethylenes, ultra-high molecular weight polyethylenes, ethylene-(meth)acrylic ester copolymers and ethylene-vinyl acetate copolymers
  • the monomer used for introducing the reactive group may be exemplified by, for example, monomers having a hydroxyl group (for example, allyl alcohol, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and the like).
  • a hydroxyl group for example, allyl alcohol, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and the like.
  • the degree of modification with the monomer containing a hydroxyl group is, relative to the olefin resin, 0.1 to 20% by weight and preferably 0.5 to 10% by weight.
  • the average molecular weight of the hydroxy modified polyolefin is not particularly limited.
  • the hydroxy modified polyolefin can be obtained by, when it has a low molecular weight, polymerizing a conjugated diene monomer with a well-known method such as anion polymerization, hydrolyzing the product and hydrogenating the obtained polymer.
  • Two or more types of these modified polyolefins may be used as combined.
  • the amount of the modified polyolefin is, relative to the total amount the polypropylene resin (A), the fiber (B) and the organic flame retardant (C) of 100 parts by weight, 0 to 10 parts by weight, preferably 0.01 to 7 parts by weight, more preferably 0.5 to 5 parts by weight, still more preferably 1 to 3 parts by weight.
  • the amount of the modified polyolefin is higher than 10 parts by weight, impact strength and economic efficiency may degrade.
  • the polypropylene resin composition of the present invention can be produced by blending, according to a well-known method, the polypropylene resin (A), the fiber (B) and the organic flame retardant (C) and, if desired, the optional component (D) in the ratio described above and undergoing a kneading step wherein these components are melt-kneaded.
  • melt-kneading is usually carried out on a mixer such as a tumbler, a V blender and a ribbon blender.
  • Melt-kneading is usually carried out on a kneading device such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, a kneader and an agitation granulator, so that (semi) melt-kneading and granulation are carried out.
  • the above components may be kneaded simultaneously or each component is separately kneaded in order to improve the properties. Namely, for example, some or all of the polypropylene resin (A) and the organic flame retardant (C), and some of the fiber (B) may be kneaded prior to kneading and granulating the remaining components.
  • the polypropylene resin composition of the present invention is preferably produced by a combining method so that the average length of the fiber (B) is 0.3 mm or more, preferably 0.4 mm or more and 2.5 mm or less in the resin composition pellets or the molded article obtained after the kneading step wherein melt-kneading is carried out.
  • the average length of the fiber (B) in the resin composition pellets or in the molded article means the value obtained by averaging the values measured on a digital microscope. Specific measurement is carried out by, when the fiber (B) is glass fiber, burning the resin composition pellets or the molded article of the present invention, mixing the ash of the glass fiber with water containing a surfactant, dropping and spreading the mixed aqueous liquid on a thin glass plate, measuring the glass fiber length on a digital microscope (Type VHX-900 from Keyence Corporation) and calculating the average.
  • a preferable production method may include, for example during melt-kneading on a twin-screw extruder, sufficiently melt-kneading polypropylene resin (A) and the organic flame retardant (C) prior to feeding the fiber (B) according to a side feed method and dispersing the sized fibers while minimizing fracture and damage to the fibers.
  • Another preferred production method may include a so-called agitation granulation method in which, for example, the polypropylene resin (A), the fiber (B) and the organic flame retardant (C) are agitated at high speed in a Henschel mixer to obtain semi-molten state while the fiber (B) in the mixture is kneaded, because this method allows easy dispersion of the fibers while minimizing fracture and damage to the fibers.
  • agitation granulation method in which, for example, the polypropylene resin (A), the fiber (B) and the organic flame retardant (C) are agitated at high speed in a Henschel mixer to obtain semi-molten state while the fiber (B) in the mixture is kneaded, because this method allows easy dispersion of the fibers while minimizing fracture and damage to the fibers.
  • Another preferred production method may include a method in which the polypropylene resin (A) and the organic flame retardant (C) except the fiber (B) are melt-kneaded in an extruder to obtain pellets which are then mixed with the above so-called "fiber (B) containing pellets” such as the glass fiber containing pellets or the carbon fiber containing pellets to produce the fiber reinforced composition, because of the same reason as described above.
  • a preferable method for producing the polypropylene resin composition of the present invention may include a method in which, in the kneading step, the components other than the fiber (B) are kneaded prior to addition of the fiber (B). Accordingly, the polypropylene resin composition of the present invention can be produced by a simple production method.
  • the molded article of the present invention can be obtained by molding the polypropylene resin composition obtained by the above method according to a well-known molding method such as injection molding (including gas injection molding, dual color injection molding, core-back injection molding and sandwich injection molding), injection compression molding (press injection), extrusion molding, sheet molding and hollow molding. Among these, injection molding or injection compression molding is preferred.
  • the polypropylene resin composition of the present invention exhibits more excellent flame retardance and drip resistance than conventionally-known flame-retardant polyolefin resins, and not only satisfies the UL94-5V Standard but also exhibits excellent mechanical properties, weather resistance and moldability.
  • the propylene polymer (X) has a long-chain branched structure and therefore remarkably improves the melt tension of the composition and exhibits the effect of drip resistance.
  • an organic flame retardant is used, and therefore, in particular, a phosphorus-containing flame retardant, especially a phosphate flame retardant thermally decomposes to give polymetaphosphoric acid, and the resultant phosphoric acid layer forms a protective layer, and in addition, as a result of the dewatering effect of polymetaphosphoric acid, the resultant carbon coating film formed could block oxygen to exhibit a flame-retardant effect.
  • the melt flow rate (MFR) of the entire polypropylene resin composition of the present invention is generally within a range of from 0.05 to 100 g/10 min, preferably from 0.1 to 50 g/10 min, more preferably from 0.3 to 30 g/10 min, even more preferably from 0.5 to 20 g/10 min, especially preferably from 1 to 10 g/10 min.
  • MFR melt flow rate
  • MFR is a value measured according to "Materials for molding and extrusion of plastic-polypropylene (PP) - Part 2: How to prepare test pieces and determine the properties thereof' in JIS K6921-2 (2005), under a test condition of 230°C and a load of 2.16 kg.
  • the polypropylene resin composition of the present invention has good flexural modulus and flexural strength and has high impact strength, and this means that the molded article thereof has good mechanical strength.
  • the polypropylene resin composition of the present invention contains as an indispensable component the polypropylene resin (X) having a long-chain branched structure, and therefore can be considered to have good and well-balanced mechanical properties.
  • the flexural modulus and flexural strength are evaluated based on the value measured at 23°C according to JIS K7203 (1995), and the Charpy impact strength (notched) is measured based on the value measured at 23°C according to JIS K7111 (2006).
  • the polypropylene resin composition of the present invention hardly discolors, and this means that the molded article thereof realizes good yellowing resistance during molding.
  • the polypropylene resin composition of the present invention contains, as indispensable components, the polypropylene resin (X) having long-chain branched structure and the organic flame retardant (C), and is characterized in that its yellowing resistance does not lower, that is, it hardly discolor (its yellowing resistance does not worsen) especially in a case where a phosphorus-containing flame retardant is used as the organic flame retardant (C).
  • the evaluation method for discoloration (yellowing resistance) in this description is as shown in the section of Examples to be given hereinunder.
  • the polypropylene resin composition and its molded article of the present invention contains the fiber (B), and therefore has extremely high flame retardance in addition to the excellent mechanical properties, weather resistance and moldability thereof, and can be favorably used for automobile parts, electric parts, container packaging parts, building parts, large-size parts, etc.
  • test pieces for flame retardance evaluation were molded and evaluated according to the UL Standard 94-5V (thickness 2.0 mmt). When the decision could not satisfy the standard of 5VA in UL94-5V, "NG" is given.
  • test pieces for flame retardance evaluation were molded and evaluated according to the UL Standard 94-V (thickness 1.5 mmt or 3.0 mmt). When the decision could not satisfy the UL Standard 94-V, "NG" is given.
  • Melt flow rate is measured according to "Materials for molding and extrusion of plastic-polypropylene (PP) - Part 2: How to prepare test pieces and determine the properties thereof' in JIS K6921-2 (test condition: 230°C, load of 2.16 kg). The unit is g/10 min.
  • a concrete measurement method in GPC employed in the present invention is as mentioned below.
  • a standard polystyrene (PS) calibration curve previously prepared is used.
  • Compounds of standard polystyrene to be used are all Tosoh's brands mentioned below.
  • F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000 0.2 mL of a solution prepared by dissolving each compound in ODCB (containing 0.5 mg/mL of BHT) so as to be 0.5 mg/mL is injected to prepare a calibration curve.
  • the calibration curve uses a cubic expression method obtained through approximation according to a least-squares method.
  • the viscosity equation [ ⁇ ] K ⁇ M ⁇ to be used in conversion into the molecular weight uses the following numerical values.
  • the resin When MT is extremely high, the resin would break at a take-up speed of 4.0 m/min. In such a case, the take-up speed is lowered, and the tension at the highest speed at which the resin could be taken out is referred to as MT.
  • the unit is gram.
  • mm fraction is determined according to the method described in paragraphs [0053] to [0065] in JP-A 2009-275207 .
  • the branching index (g') is calculated as a ratio of the limiting viscosity ([ ⁇ ]br) of a sample of the polypropylene resin (X) having a long-chain branched structure, as measured with the following Viscometer, to the limiting viscosity ([ ⁇ ]lin) of a linear polymer (Japan Polypropylene's Novatec PP (registered trademark), Grade Code: FY6), as measured separately, ([ ⁇ ]br/[ ⁇ ]lin), according to the above-mentioned method.
  • a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer)
  • Waters' Alliance GPCV 2000 is used.
  • a light-scattering detector a multiangle laser light scattering detector (MALLS), Wyatt Technology's DAWN-E is used. The detector is connected in an order of MALLS, RI and Viscometer.
  • the mobile phase solvent is 1,2,4-trichlorobenzene (with BASF's antioxidant, Irganox 1076 added in an amount of 0.5 mg/mL).
  • the flow rate is 1 mL/min, and two columns of Tosoh's GMHHR-H(S) HT are used.
  • the temperature in the column, the sample injection part and each detector is 140°C.
  • the sample concentration is 1 mg/mL, and the injection amount (sample loop volume) is 0.2175 mL.
  • the flexural modulus is measured at 23°C according to JIS K7203.
  • the dimension of the molded article is 90 ⁇ 10 ⁇ 4 mm.
  • the unit is MPa.
  • the bending strength is measured at 23°C according to JIS K7203.
  • the dimension of the molded article is 90 ⁇ 10 ⁇ 4 mm.
  • the unit is MPa.
  • the Charpy impact strength is measured at 23°C according to JIS K7111.
  • the unit is kJ/m 2 .
  • the molded test pieces are visually checked and evaluated according to the following evaluation criteria.
  • reaction liquid was poured into 500 ml of distilled water, transferred into a separating funnel, and extracted with diisopropyl ether.
  • the ether layer was washed with saturated saline water, and dried with sodium sulfate. Sodium sulfate was filtered away, the solvent was evaporated away under reduced pressure, and the residue was purified through a silica gel column to give a colorless liquid of 4-(4-i-propylphenyl)indene, 15.4 g (yield 99%).
  • reaction liquid was poured into 300 ml of water, transferred into a separating funnel, extracted three times with diisopropyl ether, and the ether layer was washed with saturated saline water and dried with sodium sulfate. Sodium sulfate was filtered away, the solvent was evaporated away under reduced pressure, and the residue was purified through a silica gel column to give 19.6 g (yield 99%) of a colorless liquid, 2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indene.
  • Racemic body ⁇ 0.95 (s, 6H), ⁇ 1.10 (d, 12H), ⁇ 2.08 (s, 6H), ⁇ 2.67 (m, 2H), ⁇ 5.80 (d 2H), ⁇ 6.37 (d, 2H), ⁇ 6.74 (dd, 2H), ⁇ 7.07 (d, 2H), ⁇ 7.13 (d, 4H), ⁇ 7.28 (s, 2H), ⁇ 7.30 (d, 2H), ⁇ 7.83 (d, 4H).
  • the resultant solid was predried one full day at 100°C in a nitrogen stream atmosphere, then coarse particles of 53 ⁇ m or more were removed, and further, this was dried under reduced pressure at 200°C for 2 hours to give 220 g of a chemically-processed smectite.
  • Triisobutylaluminium (0.84 mmol; 1.2 mL of heptane solution having a concentration of 143 mg/mL) was added to the previous 1-L flask containing the chemically-processed smectite therein, and then the solution 1 was added and stirred at room temperature for 20 minutes. Subsequently, further, triisobutylaluminium (0.36 mmol: 0.50 mL of heptane solution having a concentration of 143 mg/mL) was added, and then the above solution 2 was added and stirred at room temperature for 1 hour.
  • the internal temperature of the autoclave was made 40°C, then propylene was fed at a rate of 10 g/hr, and prepolymerized while kept at 40°C for 4 hours. Subsequently, propylene feeding was stopped, and the remaining polymerization was carried out for 1 hour. The supernatant of the resultant catalyst slurry was removed through decantation, and triisobutylaluminium (6 mmol: 17.0 mL of heptane solution having a concentration of 143 mg/mL) was added to the remaining part and stirred for 5 minutes.
  • the solid was dried under reduced pressure for 1 hour to give 52.8 g of a dry pre-polymerized catalyst.
  • the prepolymerization degree (value calculated by dividing the prepolymerized polymer amount by the solid catalyst amount) was 1.64.
  • prepolymerized catalyst 1 prepolymerized catalyst 1
  • a stirring autoclave having an inner volume of 200 liters was fully purged with propylene, and then 40 kg of fully dewatered liquefied propylene was introduced thereinto.
  • 4.4 liters (as a volume in a standard state) of hydrogen and 470 ml (0.12 mol) of triisobutylaluminium/n-heptane solution were added thereto, and the inner temperature was elevated up to 70°C.
  • 2.4 g of the prepolymerized catalyst (as a weight except the prepolymerized polymer) was introduced under pressure of argon to start polymerization, and the inner temperature was kept at 70°C.
  • 100 ml of ethanol was introduced under pressure to purge the unreacted propylene, and the autoclave was purged with nitrogen to stop the polymerization.
  • the resultant polymer was dried in a nitrogen stream atmosphere at 90°C for 1 hour to give 16.5 kg of a polymer (hereinafter referred to as "XX").
  • the catalyst activity was 6880 (g-XX/g-cat). MFR was 1.0 g/10 min.
  • pellets (X-1) were evaluated in point of the melting point, MFR, the paraxylene soluble content (CXS), 13 C-NMR, GPC (Mw/Mn and Mz/Mw), the branching index (mm), the melt tension (MT), and the rate of strain hardening in measurement of elongation viscosity ( ⁇ max (0.1)). The evaluation results are shown in Table 1.
  • D additives used were an antioxidant (D-1: BASF's IRGANOX 1010), (D-2: ADEKA's PEP 36), a neutralizing agent (D-3: NOF's calcium stearate) and a surfactant (D-4: Mitsubishi Chemical's maleic acid-modified polypropylene: CMPP2).
  • D-1 BASF's IRGANOX 1010
  • D-2 ADEKA's PEP 36
  • D-3 NOF's calcium stearate
  • surfactant D-4: Mitsubishi Chemical's maleic acid-modified polypropylene: CMPP2
  • polypropylene resin (A) long-chain branched structure-having polypropylene resin (X), polypropylene resin (Y)), the fiber (B) and the organic flame retardant (C), additional additives of the antioxidants (D-1: BASF's IRGANOX 1010) and (D-2, ADEKA's PEP36), the neutralizing agent (D-3: NOF's calcium stearate) and the surfactant (D-4: Mitsubishi Chemical's maleic acid-modified polypropylene: CMPP2) were in the ratio shown in Table 2 and Table 3, and using a high-speed stirring mixer (Henschel mixer, trade name), these were mixed at room temperature for 3 minutes.
  • D-1 BASF's IRGANOX 1010
  • D-2 ADEKA's PEP36
  • D-3 NOF's calcium stearate
  • surfactant D-4: Mitsubishi Chemical's maleic acid-modified polypropylene: CMPP2
  • the resultant mixture was melt-kneaded and extruded through a twin-screw extruder, led to pass through a cold water tank, and the strands were cut with a strand cutter to give pellets.
  • the compositional ratio of each component shown in Table 2 and Table 3 is all in terms of part by weight.
  • the ratio of the long-chain branched structure-having polypropylene resin (X) to the polypropylene resin (Y) (provided that the total of the long-chain branched structure-having polypropylene resin (X) and the polypropylene resin (Y) is 100% by weight) is shown in the parenthesis in the column of the long-chain branched structure-having polypropylene resin (X) and the polypropylene resin (Y).
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 Example 8
  • Example 9 Example 10
  • Example 12 Poly-Propylene Resin (A) long-chain branched structure-having polypropylene resin (X) X-1 19.0 (29 wt%) 13.0 (29 wt%) 19.0 (29 wt%) 13.0 (29 wt%) 15.0 (30 wt%) 22.5 (50 wt%) 31.5 (70 wt%) - 28.0 (70 wt%) 45.0 (100 wt%) 31.5 (70 wt%) 22.5 (50 wt%) X-2 (WB140) - - - - - - - 31.5 (70 wt%) - - - - X-3 - - - - - - - - - - - - - - - - - - - - - - - - - polypropylene resin (Y) Y
  • Comparative Example 1 could not prevent dripping during firing since the long-chain branched structure-having polypropylene resin (X) was not used therein, and in addition, the fiber (B) was not also used, this could not satisfy mechanical properties.
  • Comparative Example 2 could hardly prevent dripping during firing and could not realize satisfactory flame retardance, since the long-chain branched structure-having polypropylene resin (X) was not used therein.
  • the fiber (B) has good thermal conductivity, and therefore, in the absence of the fiber (B), the heat generated in firing would accumulate inside the resin so that the viscosity of the resin moiety is thereby rapidly lowered.
  • Examples 1 and 3 are compared with Comparative Example 3.
  • Comparative Example 4 does not satisfy the self-extinguishing performance, and this would be because, though the long-chain branched structure-having polypropylene resin (X) and the fiber (B) are used therein but the amount added of the organic flame retardant (C) is small.
  • Comparative Examples 5 to 7 using a resin except polypropylene are described.
  • Comparative Example 5 and Comparative Example 7 using the ABS resin the flame retardance was relatively good, but since the flowability was not good, the moldability was poor and the molding discoloration were unsatisfactory.
  • Comparative Example 6 using the polycarbonate resin all the results of flame retardance, moldability and molding discoloration were unsatisfactory.
  • the polypropylene resin composition of the present invention has excellent flame retardance in addition to excellent mechanical properties, moldability and weather resistance, and especially satisfies both self-extinguishing property and drip resistance, and therefore can attain "rating 5VA in UL94-5V" and can be favorably used for automobile parts, electric parts, container packaging parts, building components, large-size components, etc.

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Claims (5)

  1. Polypropylenharzzusammensetzung, umfassend: ein Polypropylenharz (A), welches den folgenden Erfordernissen (A-1) und (A-2) genügt; eine Faser (B), welche dem folgenden Erfordernis (B-1) genügt; und ein organisches Flammschutzmittel (C), wobei die Polypropylenharzzusammensetzung dem folgenden Erfordernis (I) genügt,
    Erfordernis (A-1):
    Das Polypropylenharz (A) enthält ein Polypropylenharz (X) mit einer langkettigen verzweigten Struktur mit den folgenden Eigenschaften (X-i) bis (X-iv):
    Eigenschaft (X-i):
    Die Schmelzflussrate (MFR) (230°C, 2,16 kg Last) beträgt von 0,1 bis 30,0 g/10 min,
    Eigenschaft (X-ii):
    Die Molekulargewichtsverteilung Mw/Mn mittels GPC beträgt von 3,0 bis 10,0 und Mz/Mw mittels GPC beträgt von 2,5 bis 10,0,
    Eigenschaft (X-iii):
    Die Schmelzspannung (MT) (Einheit: g) erfüllt eines der folgenden: log MT ≥ − 0,9 × log MFR + 0,7 oder MT ≥ 15
    Figure imgb0016
     Eigenschaft (X-iv): Der Anteil der paraxylenlöslichen Fraktion (CXS) bei 25°C beträgt weniger als 5,0 Gew.-%, bezogen auf die Gesamtmenge des Polypropylenharzes (X),
    Erfordernis (A-2):
    Das Polypropylenharz (A) enthält mindestens ein Polypropylenharz, ausgewählt aus einer Gruppe, bestehend aus dem Polypropylenharz (X) mit einer langkettigen verzeigten Struktur und einem Polypropylenharz (Y) mit den vorliegenden Eigenschaften (Y-i) bis (Y-ii):
    Eigenschaft (Y-i): Mindestens ein Polypropylenharz, ausgewählt aus einer Gruppe, bestehend aus einem Propylenhomopolymer, einem Propylen-α-Olefin-Blockcopolymer und einem statistischen Propylen-α-Olefin-Copolymer, welches nicht dem Polypropylenharz (X) mit einer langkettigen verzweigten Struktur entspricht,
    Eigenschaft (Y-ii): Das Polypropylenharz (Y) weist eine Schmelzflussrate (MFR) (230°C, 2,16 kg Last) von 1,0 bis 200 g/10 min auf,
    Erfordernis (B-1):
    Die Faser (B) ist mindestens ein Typ, ausgewählt aus einer Gruppe, bestehend aus einer Glasfaser und einer Kohlenstofffaser,
    Erfordernis (I):
    Der Gehalt jeder Komponente fällt in einen Bereich, wonach das Polypropylenharz (A) von 20 bis 77 Gewichtsteile beträgt, die Faser (B) von 5 bis 40 Gewichtsteile beträgt und das organische Flammschutzmittel (C) von 18 bis 40 Gewichtsteile beträgt, und die Gesamtmenge des Polypropylenharzes (A), der Faser (B) und des organischen Flammschutzmittels (C) 100 Gewichtsteile beträgt.
  2. Polypropylenharzzusammensetzung nach Anspruch 1, wobei das Polypropylenharz (A) weiter dem folgenden Erfordernis (A-3) genügt,
    Erfordernis (A-3):
    Das Polypropylenharz (A) enthält das Polypropylenharz (X) mit einer langkettigen verzweigten Struktur und das Polypropylenharz (Y) und das Verhältnis von diesen ist derart, dass das Polypropylenharz (X) mit einer langkettigen verzweigten Struktur von 10 bis 99 Gewichts-% und das Polypropylenharz (Y) von 1 bis 90 Gewichts-% beträgt (mit der Maßgabe, dass die Gesamtheit des Polypropylenharzes (X) mit einer langkettigen verzweigten Struktur und des Polypropylenharzes (Y) 100 Gew.-% beträgt).
  3. Polypropylenharzzusammensetzung nach Anspruch 1 oder 2, wobei das organische Flammschutzmittel (C) ein phosphorhaltiges Flammschutzmittel ist.
  4. Polypropylenharzzusammensetzung nach einem der Ansprüche 1 bis 3, wobei die Faser (B) eine Glasfaser ist.
  5. Formgegenstand, erhalten durch Formen der Polypropylenharzzusammensetzung nach einem der Ansprüche 1 bis 4.
EP14902904.3A 2014-10-01 2014-10-01 Faserverstärkte flammhemmende polypropylenharzzusammensetzung und formartikel mit verwendung davon Active EP3202841B1 (de)

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US11572462B2 (en) * 2017-02-07 2023-02-07 Exxonmobil Chemical Patents Inc. High melt strength polypropylenes with improved processability
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WO2020064752A1 (en) 2018-09-25 2020-04-02 Sabic Global Technologies B.V. Glass fiber filled flame retardant propylene composition
CN109836817B (zh) * 2019-01-28 2022-02-25 杭州本松新材料技术股份有限公司 卤素阻燃剂及其应用
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